Phenyl-substituted sulfonamides

ABSTRACT

This invention relates to 1-benzopyransulfonamides, 1-benzothiopyransulfonamides, 1-benzoxepinsulfonamides and 1-benzothiepinsulfonamides which are useful as plant growth regulants and in particular as herbicides.

This application is a divisional application of U.S. Ser. No. 641,579now U.S. Pat. No. 4,582,527, which was filed Aug. 16, 1984, which inturn is a divisional application of U.S. Ser. No. 406,191, now U.S. Pat.No. 4,492,596 filed Aug. 11, 1982.

BACKGROUND OF THE INVENTION

This invention relates to 1-benzopyransulfonamides,1-benzothiopyransulfonamides, 1-benzoxepinsulfonamides and1-benzothiepinsulfonamides which are useful as plant growth regulantsand in particular as herbicides.

Netherlands Pat. No. 121,788, published Sept. 15, 1966, discloses thepreparation of compounds of the following Formula and their use asgeneral or selective herbicides: ##STR1## wherein R₁ and R₂ mayindependently be alkyl of 1-4 carbon atoms; and

R₃ and R₄ may independently be hydrogen, chlorine or alkyl of 1-4 carbonatoms.

U.S. Pat. No. 3,637,366 discloses compounds having the formula: ##STR2##wherein R₁ is hydrogen or lower saturated aliphatic acyl and

R₂ is hydrogen, 2-pyrimidinyl, pyridyl, amidino, acetyl or carbamoyl.

The disclosed compounds are said to provide control of crabgrass, cress,endive, clover and Poa annua.

French Pat. No. 1,468,747 discloses the following para-substitutedphenylsulfonamides as being useful as antidiabetic agents: ##STR3##wherein R=H, halogen, CF₃ or alkyl.

Logemann et al., Chem. Ab., 53, 18052g (1959), disclose a number ofsulfonamides, including uracil derivatives and those having the formula:##STR4## wherein R is butyl, phenyl or ##STR5## and R₁ is hydrogen ormethyl.

When tested for hypoglycemic effect in rats (oral doese of 25 mg/100 g),the compounds in which R is butyl and phenyl were most potent. Theothers were of low potency or inactive.

Wojciechowski, J. Acta. Polon. Pharm. 19, p. 121-5 (1962) [Chem. Ab., 591633 e] describes the synthesis ofN-[(2,6-dimethoxypyrimidin-4-yl)aminocarbonyl]-4-methylbenzenesulfonamide:##STR6##

U.S. Pat. No. 4,127,405 teaches compounds which are useful forcontrolling weeds in wheat having the formula ##STR7## wherein R is##STR8## R₁ is ##STR9## R₃ and R₆ are independently hydrogen, fluorine,chlorine, bromine, iodine, alkyl of 1-14 carbon atoms, alkoxy of 1-4carbon atoms, nitro, trifluoromethyl, cyano, CH₃ S(O)_(n) -- or CH₃ CH₂S(O)_(n) --;

R₄ is hydrogen, fluorine, chlorine, bromine or methyl;

R₅ is hydrogen, fluorine, chlorine, bromine, methyl or methoxy;

R₇ is hydrogen, fluorine, chlorine, bromine, alkyl of 1-2 carbon atomsor alkoxy of 1-2 carbon atom;

R₈ is hydrogen, methyl, chlorine or bromine;

R₉ and R₁₀ are independently hydrogen, methyl, chlorine or bromine;

W and Q are independently oxygen or sulfur;

n is 0, 1 or 2;

X is hydrogen, chlorine, bromine, methyl, ethyl, alkoxy of 1-3 carbonatoms, trifluoromethyl, CH₃ S-- or CH₃ OCH₂ --; and

Z is methyl or methoxy;

or their agriculturally suitable salts; provided that:

(a) when R₅ is other than hydrogen, at least one of R₃, R₄, R₆ and R₇ isother than hydrogen and at least two of R₃, R₄, R₆ and R₇ must behydrogen;

(b) when R₅ is hydrogen and all of R₃, R₄, R₆ and R₇ are other thanhydrogen, then all of R₃, R₄, R₆ and R₇ must be either chlorine ormethyl; and

(c) when R₃ and R₇ are both hydrogen, at least one of R₄, R₅ or R₆ mustbe hydrogen.

In addition, U.S. Ser. No. 227,886 now abandoned teacheso-alkylsulfonylbenzenesulfonylureas which are useful as herbicides.

In U.S. Ser. No. 274,233, now U.S. Pat. No. 4,391,627 there is adisclosure of herbicidal benzo[b]thiophene- and benzofuransulfonylureasin which the sulfonylureido group is bonded to the heterocyclic ring.

In U.S. Ser. No. 363,379, now U.S. Pat. No. 4,562,882 there is adisclosure of herbicidal benzodioxole- and benzodioxansulfonylureas,while in U.S. Ser. No. 312,183, now abandoned herbicidal benzofuran- andbenzothiophenesulfonylureas are disclosed in which thiosulfonylureidogroup is bonded to the benzo ring.

Undersired vegetation can cause substantial damage to useful crops,especially agricultural products that satisfy man's basic food and fiberneeds, such as cotton, rice, corn, wheat, soybean and the like.

Although a wide variety of materials are available which can be used forkilling or inhibiting (controlling) the growth of undesired vegetationthe need exists for still more effective herbicides that destroy orcontrol weeds without causing significant damage to useful crops.

SUMMARY OF THE INVENTION

This invention relates to compounds of Formula I, agriculturalcompositions containing them and their method-of-use as general orselective pre-emergent or post-emergent herbicides or plant growthregulants. ##STR10## wherein J is ##STR11## Q is O, S or SO₂ ; R is H orCH₃ ;

R₁ is H, CH₃, OCH₃, Cl, Br, CO₂ R₅, SO₂ R₆, OSO₂ R₇ or SO₂ NR₈ R₉ ;

R₄ is H or CH₃ ;

R₂ and R₃ are independently H or C₁ -C₃ alkyl;

R₅ is C₁ -C₃ alkyl, CH₂ CH═CH₂, CH₂ CH₂ OCH₃ or CH₂ CH₂ Cl;

R₆ is C₁ -C₃ alkyl;

R₇ is C₁ -C₃ alkyl or CF₃ ;

R₈ and R₉ are independently C₁ -C₂ alkyl;

A is ##STR12## X is CH₃, OCH₃ or Cl; Y is CH₃, OCH₃, OC₂ H₅, CH₂ OCH₃,C₂ H₅, NH₂, NHCH₃ or N(CH₃)₂ ;

Z is CH or N;

G is O or CH₂ ; and

X₁ is CH₃, OCH₃ or OC₂ H₅ ;

and their agriculturally suitable salts; provided that:

(1) when X is Cl, then Z is CH and Y is OCH₃, NH₂, NHCH₃, N(CH₃)₂ or OC₂H₅ ;

(2) the total number of carbon atoms in R₂ and R₃ are less than or equalto 3;

(3) in Formula J₂, when R₂ and R₃ are other than H, then R₄ is H;

(4) in Formula J₃, when R₂ is other than H, then R₄ is H;

(5) when Q is S, then R₁ is not SO₂ NR₈ R₉ ;

(6) in Formulae J₃ and J₆, Q may not be O; and

(7) in Formula J₇, R₁ is not CH₃.

Preferred for reasons of their higher herbicidal activity, greater plantgrowth regulant activity, or more favorable ease of synthesis are:

(1) Compounds of Formula I where J is J₁.

(2) Compounds of preferred 1 where R is H.

(3) Compounds of preferred 2 where R₁ is H.

(4) Compounds of preferred 3 where A is ##STR13## and X is OCH₃ or Cl.(5) Compounds of preferred 4 where Y is CH₃ or OCH₃.

(6) Compounds of Formula I where J is J₂.

(7) Compounds of preferred 6 where R is H.

(8) Compounds of preferred 7 where R₁ is H.

(9) Compounds of preferred 8 where A is ##STR14## and X is OCH₃ or Cl.(10) Compounds of preferred 9 where Y is CH₃ or OCH₃.

(11) Compounds of Formula I where J is J₃.

(12) Compounds of preferred 11 where R is H.

(13) Compounds of preferred 12 where R₁ is H.

(14) Compounds of preferred 13 where A is ##STR15## and X is OCH₃ or Cl.(15) Compounds of preferred 14 where Y is CH₃ or OCH₃.

(16) Compounds of Formula I where J is J₄.

(17) Compounds of preferred 16 where R is H.

(18) Compounds of preferred 17 where R₁ is H.

(19) Compounds of preferred 18 where A is ##STR16## and X is OCH₃ or Cl.(20) Compounds of preferred 19 where Y is CH₃ or OCH₃.

(21) Compounds of Formula I where J is J₅.

(22) Compounds of preferred 21 where R is H.

(23) Compounds of preferred 22 where R₁ is H.

(24) Compounds of preferred 23 where A is ##STR17## and X is OCH₃ or Cl.(25) Compounds of preferred 24 where Y is CH₃ or OCH₃.

(26) Compounds of Formula I where J is J₆.

(27) Compounds of preferred 26 where R is H.

(28) Compounds of preferred 27 where R₁ is H.

(29) Compounds of preferred 28 where A is ##STR18## and X is OCH₃ or Cl.(30) Compounds of preferred 29 where Y is CH₃ or OCH₃.

(31) Compounds of Formula I where J is J₇.

(32) Compounds of preferred 31 where R is H.

(33) Compounds of preferred 32 where R₁ is H.

(34) Compounds of preferred 33 where A is ##STR19## and X is OCH₃ or Cl.(35) Compounds of preferred 34 where Y is CH₃ or OCH₃.

Specifically preferred for reasons of their highest herbicidal activity,greatest plant growth regulant activity and/or most favorable ease ofsynthesis are:

•N-[(4-methoxy-6-methylpyrimidin-2-yl)aminocarbonyl]-3,4-dihydro-2H-1-benzothiopyran-8-sulfonamide,1,1-dioxide;

•N-[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]-3,4-dihydro-2H-1-benzothiopyran-8-sulfonamide,1,1-dioxide; and

•N-[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)aminocarbonyl]-3,4-dihydro-2H-1-benzothiopyran-8-sulfonamide,1,1-dioxide.

DETAILED DESCRIPTION OF THE INVENTION

Synthesis

The compounds of Formula (I) can be prepared by methods described belowin Equations 1, 2 and 3.

As shown in Equation 1, compounds of Formula (I) can be prepared byreacting a sulfonylcarbamate of Formula (II) with an appropriate amineof Formula (III). J, R and A are as previously defined. ##STR20##

The reaction is carried out at 50°-100° C. in a solvent such as dioxanefor 1/2 to 24 hours as taught in EPO Publication No. 44807. The requiredcarbamates (II) are prepared by reacting the corresponding sulfonamides(IV) with diphenylcarbonate in the presence of a strong base.

Alternatively, as shown in Equation 2, compounds (I), where R₁ is otherthan CO₂ R₅, can be prepared by reacting sulfonamides of Formula (IV)with an appropriate methylcarbamate of Formula (V) in the presence of anequimolar amount of trimethylaluminum. ##STR21##

The reaction is carried out at 25° to 40° C. in a solvent such asmethylene chloride for 10 to 96 hours under an inert atmosphere astaught in U.S. Ser. No. 337,934.

The compounds of Formula (I) where J is J₁, J₄ and J₇ for all values ofQ and J₂, J₃, J₅ and J₆ when Q is SO₂ can be prepared by reactingsulfonylisocyanates of Formula (VI) with an appropriate amine of Formula(III) as shown in Equation 3. ##STR22##

The reaction is carried out at 25° to 40° C. in an inert aprotic solventsuch as methylene chloride for 0.5 to 24 hours as taught in U.S. Pat.No. 4,127,405. The intermediate sulfonylisocyanates (VI) can be preparedfrom the appropriate sulfonamides (IV) by the reaction with phosgene, inthe presence n-butylisocyanate and a tertiary amine catalyst, at refluxin a solvent such as xylene by the method of U.S. Pat. No. 4,238,621.

Alternatively, the sulfonylisocyanates can be prepared from thesulfonamides by a two step procedure involving (a) reacting thesulfonamides with n-butylisocyanate in the presence of a base such as K₂CO₃ at reflux in an inert solvent such as 2-butanone forming an-butylsulfonylurea; and (b) reacting this compound with phosgene and atertiary amine catalyst at reflux in xylene solvent. The method issimilar to a procedure taught by Ulrich and Sayigh, Newer Methods ofPreparative Organic Chemistry, Vol. VI, p. 223-241, Academic Press, NewYork and London, W. Foerst Ed.

The sulfonamides of Formula IV in Equations 1, 2 and 3 are importantintermediates for the preparation of the compounds of this invention.The synthesis of the required sulfonamide intermediates are described inEquations 4, 5 and 6.

As shown in Equation 4, sulfonamides of Formula IV, where J is J₁, J₂,J₄, J₅ and J₇ for all Q, can be prepared from the corresponding sulfonylchlorides of Formula VII. ##STR23##

The preparation of sulfonamides from ammonium hydroxide and sulfonylchlorides is widely reported in the literature, e.g., Crossley et al.,J. Am. Chem. Soc., 60, 2223 (1938) and Pailer, Monatsh., 92, 677 (1961).Preparation utilizing the reaction of sulfonyl chlorides with an excessof anhydrous ammonia at 0° C. in ethyl ether or chlorobutane is alsoknown.

The sulfonyl chlorides VII can be prepared from the appropriate amineVIII by diazotization with sodium nitrite in HCl, followed by reactionof the diazonium salt with sulfur dioxide and cupric chloride in aceticacid analogous to the teachings of Yale and Sowinski, J. Org. Chem., 25,1824 (1960).

Alternatively, sulfonyl chlorides of Formula VII can be prepared by amodification of the above procedure whereby the diazotization reactionis carried out in dilute sulfuric acid and the resulting diazonium saltis reacted with sulfur dioxide, HCl and cupric chloride in a cosolventmixture consisting of acetic acid-water (1:1) and an immiscible, inertsolvent such as 1-chlorobutane or methylene chloride at 0°-40° C. for 1to 24 hours as disclosed by the teachings of U.S. Ser. No. 345,935.

Sulfonamides of Formula IVa, where n is 1 or 2, are prepared from theircorresponding saturated analogs IVb as shown in Equation 5. R₁, R₂, andR₄ are as previously defined. When n is 2, R₄ is H. ##STR24##

The reaction is carried out by contacting the saturated sulfide with oneequivalent of a suitable oxidizing agent such as hydrogen peroxide in asolvent such as acetic acid to produce the corresponding sulfoxide. Thesulfoxide is then heated with acetic anhydride with or without acosolvent at 50° to 140° C. for 2 to 24 hours. This is similar to themethod taught by Parham and Koncos, J. Amer. Chem. Soc., 83, 4034 (1961)for the preparation of 4H-1-benzothiopyran.

Sulfonamides of Formula IVc where n is 0 or 1 can also be prepared fromthe corresponding saturated analogs IVd by the two step sequence shownin Equation 6. R₁, R₂, R₃, R₄ and Q are as previously described exceptthat R₁ is not CH₃. When n is 1, R₄ is H. ##STR25##

The first step involves benzylic bromination by N-bromosuccinimide inrefluxing carbon tetrachloride to give a monobromo derivative. Themonobromide is dehydrobrominated in the second step by contacting with asuitable base such as DABCO or ethoxide in an inert solvent such asbenzene. This method has been used to prepare 2H-1-benzopyran fromdihydrobenzopyran (Clemo and Ghatge, J. Chem. Soc., 4347 (1955)).

Applying the above procedure a second time to the compounds IVc where nis 1, Q is SO₂ and R₃ is H will provide sulfonamides IV where J is J₇,as taught by Traynelis and Love, J. Org. Chem., 26, 2728 (1961).

Finally, sulfonamides of Formula IV where Q is SO₂ can be prepared fromthe appropriate sulfonamides IV where Q is S by a variety of standardliterature procedures with m-chloroperbenzoic acid (Johnson et. al.,Tetrahedron 25, 5649 (1969), or with aqueous hydrogen peroxide in aceticacid (Bordwell et. al., J. Amer. Chem. Soc., 77, 1141 (1955)).

The amines of Formula VIII in Equation 4, where J is J₁, J₂, J₄, J₅ andJ₇ for all Q, can be prepared by reduction of the corresponding nitrocompounds of Formula IX, as shown in Equation 7. ##STR26##

The reduction of nitro compounds to amines can be carried out by any ofseveral known methods as described in Preparative Organic Chemistry, 4Ed., p. 557-563, John Wiley and Sons, New York and London, G. Hilgetagand A. Martini Ed.

Alternatively, the amines of Formula VIIIa can be prepared by athioClaisen rearrangement of an appropriate allyl phenylthio ether X asoutlined in Equation 8. R₁, R₂, R₃ and R₄ are as previously defined.##STR27##

The rearrangements are carried out at 180° to 250° C. for 0.5 to 24hours either neat or in the presence of a high boiling amine solventsuch as quinoline or diethylaniline as taught by S. J. Rhoads and N. R.Raulins, Organic Reactions, Vol. 22, p. 1-252, John Wiley and Sons, NewYork and London, W. G. Dauben, Editor in Chief. In certain cases, the6-ring fused product VIIIa is accompanied by a 5-ring fused isomer. Thedesired amine VIIIa can be separated by either fractionalcrystallization, fractional distillation or by a chromatographic method.The starting allylphenylthio ethers X can be prepared from theappropriate aminothiophenols by methods known to one skilled in the art.

The preparation of the nitro compounds of Formula IX in Equation 7 whereJ is either J₁ and J₄ or J₂ and J₅ and R₁ is H, CH₃, OCH₃, Cl or Br isoutlined in Equation 9. The two routes utilize a common nitro ketoneintermediate XI; R₂, R₃, R₄ and Q are as previously defined and n is 0or 1; when n is 1, R₄ is H. ##STR28##

The saturated nitro compounds of Formula Xa are prepared by selectivelyreducing the tosylhydrozone derivative of nitro ketone XI withcatecholborane in a solvent such as chloroform for 2 to 24 hours atambient temperatures according to the teachings of Kabalka and Chandler,Synthetic Commun., 9, 275 (1979).

Alternatively, ketone XI can be reduced directly to give thecorresponding alcohol which is then dehydrated by one of a variety ofknown methods such as P₂ O₅ by one skilled in the art.

The nitro compounds of Formula IX in Equation 7 where J is J₁ and J₄ andR₁ is CO₂ R₅, SO₂ R₆, OSO₂ R₇ or SO₂ NR₈ R₉ are prepared from thecorresponding compounds IXc (from Equation 9, compounds IXa where R₁ isCl) as shown in Equation 10. R₂, R₃ and R₄ are as previously defined, Qis O or S and n is 0 or 1; when n is 1, and R₄ is H. ##STR29##

As shown in Equation 10, the chloronitro compounds IXc are contactedwith a reagent or reagents, to be discussed below, to form compounds IXacontaining the desired R₁ group.

The nitro compounds of Formula IXa where R₁ is SO₂ R₆ are prepared inone step by reacting IXc with an appropriate sulfinic acid salt in asolvent such as dimethylformamide at 25° to 80° C. for 1 to 24 hours.Such displacements are reviewed in Organic Chemistry of Sulfur, p.536-539, Plenum Press, New York and London, 1977, S. Oae, Ed.Alternatively, IXc can be reacted with an appropriate thiol in thepresence of a suitable base such as sodium hydride or potassiumhydroxide under the conditions described above to give an intermediatesulfide of Formula IXa where R₁ is SR₆. The sulfide is then oxidized tothe desired compounds IXa where R₁ is SO₂ R₈ and Q is O or SO₂ bymethods known to one skilled in the art.

The nitro compounds of Formula IXa where R₁ is SO₂ NR₈ R₉ and Q is O orSO₂ are prepared in two steps starting from an intermediate sulfide (IXawhere R₁ is SR₆) prepared as described above. The sulfide is reactedwith molecular chlorine in aqueous acetic acid at 10° to 50° C. for 0.5to 4 hours to give the corresponding sulfonyl chloride IXa where R₁ isSO₂ Cl as taught by Langler, Can. J. Chem., 54, 498 (1976) and Langlerand Grossert, Can. J. Chem., 55, 407 (1977). The sulfonyl chloride isthen contacted with an excess of an appropriate dialkyl amine in aninert solvent such as tetrahydrofuran by methods known to one skilled inthe art.

The nitro compounds of Formula IXa where R₁ is OSO₂ R₇ can be preparedin two steps by first heating IXc with one equivalent of a strong basesuch as sodium or potassium hydroxide in dimethylformamide at 25° to 80°C. for 1 to 8 hours to form an intermediate compound IXa where R₁ is OH.This intermediate is reacted with an appropriate sulfonyl chloride R₈SO₂ Cl or the appropriate anhydride in the presence of a base such astriethyl amine in an inert solvent such as methylene chloride at 0° to40° C. for 1 to 24 hours.

The nitro compounds of Formula IXa where R₁ is CO₂ R₅ can be prepared inthree steps by first reacting IXc with one equivalent of potassiumcyanide in dimethylformamide at 25° to 80° C. for 1 to 8 hours to forman intermediate compound IXa where R₁ is CN. This intermediate can behydrolized by heating in a strong acid such as HCl in a solvent such asacetic acid to form a carboxylic acid which can then be converted to itscorresponding esters by methods known to one skilled in the art.

The nitro compounds of Formula IX in Equation 7 where J is J₂ and J₅(Formula IXb in Equation 9) and R₁ is CO₂ R₅, SO₂ R₆, OSO₂ R₇ or SO₂ NR₈R₉ are prepared from the corresponding saturated analogs IXa by thebromination/dehydrobromination sequence described earlier forsulfonamides IVc in Equation 6. This procedure can also be used toprepare compounds of Formula IXb where R₁ is H, OCH₃, Cl or Br. Whenthis procedure is applied a second time to compounds IXb where n is 1, Qis SO₂ and R₃ and R₄ are H, the nitro compounds of Formula IX where J isJ₇ are obtained.

Finally, the nitro compounds of Formula IX in Equation 7 where Q is SO₂can be prepared from the corresponding nitro compound IX where Q is S bymethods discussed earlier for sulfonamides IV.

Several of the nitro compounds of Formula IX are known, for example8-nitro-3,4-dihydro-2H-1-benzopyran (Bowie and Chai, Aust. J. Chem., 30,675 (1977)), and 8-nitro-2H-1-benzopyran (Box and McCaw, Rev. Latinoam.Quim, 10, 118, (1979)).

The nitro ketones of Formula IX in Equation 10 where R₁ is H, CH₃, OCH₃,Cl or Br are prepared by cyclization of the appropriate carboxylic acidXII as shown in Equation 11. R₂, R₃ and R₄ are as previously defined, Qis O or S and n is 0 or 1, when n is 1, R₄ is H. ##STR30##

The reaction is carried out by heating the acid with a suitablecondensing agent such as polyphosphoric acid, hydrofluoric acid,sulfuric acid or stannic chloride or the acid may be converted to itschloride and heated with a typical Friedel-Crafts reagent such asaluminum chloride or stannic chloride. For a comprehensive review ofthis and related reactions, see "Friedel-Crafts and Related Reactions"Vols. 1-4, Interscience, New York and London, G. A. Olah, Ed.

In cases where R₂ does not equal R₃, and R₄ is other than H, isomericmixtures may result. These mixtures can be used in subsequent reactionsor separated by fractional crystallization or chromatographic methods.

The starting nitro carboxylic acids XII can be prepared by reacting anappropriate nitrophenol or nitrothiophenol with the appropriateβ-bromopropionate or γ-bromobutyrate in the presence of base by methodsknown to one skilled in the art. The preparation of benzopyrans,benzothiopyrans, benzoxepin and benzothiepin from substituted phenolsand thiophenols are widely reported in the literature. For generalreviews see "Chromans and Tocopherols", The Chemistry of HeterocyclicCompounds, Vol. 36, John Wiley and Sons, New York, 1981, G. P. Ellis,Ed.; "Chromenes, Chromanones and Chromones", The Chemistry ofHeterocyclic Compounds, Vol. 31, John Wiley and Sons, New York, 1977, G.P. Ellis, Ed.; "Seven-Membered Heterocyclic Compounds Containing Oxygenand Sulfur", The Chemistry of Heterocyclic Compounds, Vol. 26, JohnWiley and Sons, New York, 1972, A. Rosowsky, Ed.; "Polycyclic Five- andSix-Membered Compounds Containing One O or S Atom", HeterocyclicCompounds, Vol. 2, John Wiley and Sons, New York, 1951, R. C.Elderfield, Ed. For a most recent review on the Synthesis and Reactionsof 4-Chromanones, see: Kabbe and Widdig, Angew Chem. Int. Ed. Engl., 21,247 (1982).

The amines of Formula III in Equations 1 and 3 and the carbamates ofFormula V in equation 2 are also important intermediates for thepreparation of the compounds of this invention and can be prepared bymethods taught in U.S. Ser. No. 345,935.

Agriculturally suitable salts of compounds of Formula I are also usefulherbicides and can be prepared in a number of ways known to the art. Forexample, metal salts can be made by treating compounds of Formula I witha solution of an alkali or alkaline earth metal salt having asufficiently basic anion (e.g., hydroxide, alkoxide, carbonate orhydride). Quaternary amine salts can be made by similar techniques.

Salts of compounds of Formula I can also be prepared by exchange of onecation for another. Cationic exchange can be effected by directtreatment of an aqueous solution of a salt of a compound of Formula I(e.g., alkali metal or quaternary amine salt) with a solution containingthe cation to be exchanged. This method is most effective when thedesired salt containing the exchanged cation is insoluble in water,e.g., a copper salt, and can be separated by filtration.

Exchange may also be effected by passing an aqueous solution of a saltof a compound of Formula I (e.g., an alkali metal or quaternary aminesalt) through a column packed with a cation exchange resin containingthe cation to be exchanged. In this method, the cation of the resin isexchanged for that of the original salt and the desired product iseluted from the column. This method is particularly useful when thedesired salt is water-soluble, e.g., a potassium, sodium or calciumsalt.

Acid addition salts, useful in this invention, can be obtained byreacting a compound of Formula I with a suitable acid, e.g.,p-toluenesulfonic acid, trichloroacetic acid or the like.

EXAMPLE 1

8-Amino-2H-1-benzothiopyran

(2-Aminophenyl)allylsulfide (55 g) was heated at 250° C. for 1 hour,cooled, and then the product was distilled through a 20 cm jacketedspinning band column using a 5:1 reflux ratio. The fraction distillingat 88°-90° C. at 0.25 mmHg was collected (13.3 g) and shown to beapproximately 90% pure 8-aminobenzothiopyran by NMR analysis.

90 MHz NMR (CDCl₃)δ: 7.0-6.3 (m, 3H, arom); 3.7 (br, 2H, NH₂); 3.0 (m,2H, CH₂); 2.7 (m, 2H, CH₂); and 2.0 (m, 2H, CH₂).

IR (neat) 3350, 3300 and 1600 cm⁻¹.

EXAMPLE 2

8-Acetamido-2H-1-benzothiopyran

To a solution of 21.1 g of 8-amino-2H-1-benzothiopyran in 200 ml of1-chlorobutane was added a solution of 13.3 ml of acetic anhydride in 50ml of 1-chlorobutane. The temperature of the mixture rose during theaddition and the mixture was refluxed for an additional 30 minutes. Thesolution was cooled in ice and filtered to give 18.0 g of the desiredacetamide as colorless needles, m.p. 133°-135° C. The mother liquor wasconcentrated to ˜1/5 volume to give a second crop of 4.1 g, m.p.133°-135° C.

90 MHz NMR (CDCl₃)δ: 8.0-6.8 (m, 4H, arom--NH); 3.0 (m, 2H, CH₂); 2.8(m, 2H, CH₂); and 2.1 (s and m, 5H, CH₃ and CH₂).

IR (nujol) 3100 and 1630 cm⁻¹.

EXAMPLE 3

8-Acetamino-2H-1-benzothiopyran, 1,1-dioxide

To a solution of 21.0 g of 8-acetamino-2H-1-benzothiopyran in 100 ml ofglacial acetic acid was added 60 ml of 30% H₂ O₂ in water. The additionwas accompanied by an exotherm to 70° C. and the temperature was held at70° C. for an additional hour. The solution was cooled, diluted withwater and extracted with methylene chloride. The extract was washed withwater, saturated sodium bisulfite and brine, dried over MgSO₄ andconcentrated to give 23 g of an orange oil. The oil was dissolved in 50ml of hot 1-chlorobutane and allowed to cool to give 18.0 g of thedesired dioxide as orangish-white crystals, m.p. 98°-100° C.

90 MHz NMR (CDCl₃)δ: 9.2 (br, 1H, NH); 8.3 (d, J=8 Hz, 1H, arom); 7.4(t, J=8 Hz, 1H, arom); 7.0 (d, J=8 Hz, 1H, arom); 3.4 (m, 2H, CH₂); 3.0(m, 2H, CH₂); 2.5 (m, 2H, CH₂); and 2.2 (s, 3H, CH₃).

IR (nujol) 3300 and 1690 cm⁻¹.

EXAMPLE 4

8-Amino-2H-1-benzothiopyran, 1,1-dioxide Hydrochloride

A solution of 17.5 g of 8-acetamino-2H-1-benzothiopyran, 1,1-dioxide in100 ml of concentrated HCl was heated at 80°-95° C. for 1 hour, cooledin ice and filtered to give a white solid which was washed with etherand air dried to give 14.7 g of the free amine as its hydrochloridesalt, m.p. 205°-209° C.

90 MHz NMR (TFA)δ: 7.9-7.5 (m, 3H, arom); 3.7 (m, 2H, CH₂); 3.2 (m, 2H,CH₂); and 2.7 (m, 2H, CH₂).

IR (nujol) 3200-2300 cm⁻¹.

EXAMPLE 5

2H-1-Benzothiopyran-8-sulfonamide, 1,1-dioxide

To a suspension of 14.0 g of 8-amino-2H-1-benzothiopyran, 1,1-dioxidehydrochloride cooled to -5° C. in 25 ml of concentrated HCl and 25 ml ofglacial acetic acid was added a solution of 4.55 g of sodium nitrite in10 ml of water at such a rate that the reaction temperature did not riseabove 5° C. The mixture was stirred at 0° C. for 30 minutes then addeddropwise to a solution of 50 ml of concentrated HCl, 50 ml of glacialacetic acid, 2.0 g of CuCl₂.2H₂ O and 8 ml of liquified SO₂ cooled to-5° C. The mixture was stirred at 0° C. for 1 hour and at 20° C. for 2hours during which time gas evolution was noted. The mixture was dilutedwith 400 ml of water and the resulting solid was filtered, washed withwater and air dried. The solid was suspended in 250 ml of methylenechloride and contacted with 4 ml of liquified ammonia at -5° C. Thesuspension was stirred at room temperature for 65 hours, concentrated toa white powder, suspended in 100 ml of 1N HCl and filtered to give thesulfonamide as a white solid, 14.5 g, m.p. 214°-216° C. (wet). 13.5 g ofthe wet sulfonamide was suspended in xylene and refluxed under adean-stark trap to remove water. Cooling and filtration gave 11.5 g ofthe sulfonamide as a white solid, m.p. 239°-241° C.

90 MHz NMR (CDCl₃ +DMSO)δ: 8.2 (m, 1H, arom); 7.7-7.5 (m, 2H, arom); 7.1(br, 2H, SO₂ NH₂); 3.7-3.1 (m, 4H, CH₂ 's); and 2.5 (m, CH₂ +DMSOsolvent peak).

IR (nujol) 3300, 3200, 1330 and 1170 cm⁻¹.

EXAMPLE 6

2H-1-Benzothipyran-8-sulfonylisocyanate, 1,1-dioxide

A solution of 8.0 g of 2H-1-benzothipyran-8-sulfonamide, 1,1-dioxide and6.0 ml of n-butylisocyanate in 100 ml of 2-butanone was refluxed in thepresence of 6.0 g of K₂ CO₃ for 16 hours. The mixture was cooled, pouredinto 500 g of ice-water, acidified with 10% HCl and extracted withmethylene chloride. The extract was dried over MgSO₄ and concentrated togive 10.2 g of the crude n-butylurea as an amber oil which solidified onstanding. The crude urea was dissolved in 200 ml of dry xylenescontaining 0.2 g of DABCO and 4.0 ml of n-butylisocyanate and heated to138° C. The mixture was contacted with 4.0 ml of phosgene at such a ratethat the temperature remained between 132° to 138° C. The solution wasrefluxed for an additional hour, cooled to 25° C., filtered undernitrogen and concentrated to give the crude sulfonylisocyanate as anoil. IR (neat) 2230 cm⁻¹. The crude sulfonylisocyanate was diluted to120 ml with dry methylene chloride to give a stock solution for use insubsequent reactions.

EXAMPLE 7

N-[(4-Methoxy-6-methylpyrimidin-2-yl)aminocarbonyl]-2H-1-benzopyran-8-sulfonamide,1,1-dioxide

0.35 g of 2-amino-4-methoxy-6-methylpyrimidine was added to 20 ml of thesulfonylisocyanate stock solution (ca. 1.3 g of the sulfonylisocyanate)prepared in Example 6 and the mixture stirred for 16 hours at 25° C. Thesolution was triturated with 1-chlorobutane and the crystals whichformed were filtered to give 0.13 g of the desired urea, m.p. 217°-220°C.

90 MHz NMR (CDCl₃ +DMSO)δ: 13.4 (br, 1H, NH); 9.8 (br, 1H, NH); 8.4 (m,1H, arom); 7.8-7.5 (m, 2H, arom); 6.3 (s, 1H, CH); 4.0 (s, 3H, OCH₃);3.5-3.0 (m, CH₂ 's); 2.6-2.3 (m, CH₂ +DMSO solvent peak); and 2.4 (s,CH₃).

IR (nujol) 1700 cm⁻¹

Using the procedures of Examples 1-7, the following compounds may beprepared.

                                      TABLE Ia                                    __________________________________________________________________________     ##STR31##                                                                    n Q  R  R.sub.1    R.sub.2                                                                              R.sub.3                                                                              R.sub.4                                                                          X   Y     Z  m.p. (°)              __________________________________________________________________________    0 O  H  H          H      H      H  CH.sub.3                                                                          CH.sub.3                                                                            CH                              0 O  H  H          H      H      H  CH.sub.3                                                                          OCH.sub.3                                                                           CH                              0 O  H  H          H      H      H  OCH.sub.3                                                                         OCH.sub.3                                                                           CH                              0 O  H  H          H      H      H  CH.sub.3                                                                          CH.sub.3                                                                            N                               0 O  H  H          H      H      H  CH.sub.3                                                                          OCH.sub.3                                                                           N                               0 O  H  H          H      H      H  OCH.sub.3                                                                         OCH.sub.3                                                                           N                               0 S  H  H          H      H      H  CH.sub.3                                                                          CH.sub.3                                                                            CH                              0 S  H  H          H      H      H  CH.sub.3                                                                          OCH.sub.3                                                                           CH                              0 S  H  H          H      H      H  OCH.sub.3                                                                         OCH.sub.3                                                                           CH                              0 S  H  H          H      H      H  CH.sub.3                                                                          CH.sub.3                                                                            N                               0 S  H  H          H      H      H  CH.sub.3                                                                          OCH.sub.3                                                                           N                               0 S  H  H          H      H      H  OCH.sub.3                                                                         OCH.sub.3                                                                           N                               0 SO.sub.2                                                                         H  H          H      H      H  CH.sub.3                                                                          CH.sub.3                                                                            CH 214-216°              0 SO.sub.2                                                                         H  H          H      H      H  CH.sub.3                                                                          OCH.sub.3                                                                           CH 217-220°              0 SO.sub.2                                                                         H  H          H      H      H  OCH.sub.3                                                                         OCH.sub.3                                                                           CH 208-216°              0 SO.sub.2                                                                         H  H          H      H      H  CH.sub.3                                                                          CH.sub.3                                                                            N                               0 SO.sub.2                                                                         H  H          H      H      H  CH.sub.3                                                                          OCH.sub.3                                                                           N  214-218°              0 SO.sub.2                                                                         H  H          H      H      H  OCH.sub.3                                                                         OCH.sub.3                                                                           N                               0 O  H  H          CH.sub.3                                                                             H      H  CH.sub.3                                                                          CH.sub.3                                                                            CH                              0 O  H  H          CH.sub.3                                                                             H      H  CH.sub.3                                                                          OCH.sub.3                                                                           CH                              0 O  H  H          CH.sub.3                                                                             H      H  OCH.sub.3                                                                         OCH.sub.3                                                                           CH                              0 O  H  H          CH.sub.3                                                                             H      H  CH.sub.3                                                                          CH.sub.3                                                                            N                               0 O  H  H          CH.sub.3                                                                             H      H  CH.sub.3                                                                          OCH.sub.3                                                                           N                               0 O  H  H          CH.sub.3                                                                             H      H  OCH.sub.3                                                                         OCH.sub.3                                                                           N                               0 S  H  H          CH.sub.3                                                                             H      H  CH.sub.3                                                                          CH.sub.3                                                                            CH                              0 S  H  H          CH.sub.3                                                                             H      H  CH.sub.3                                                                          OCH.sub.3                                                                           CH                              0 S  H  H          CH.sub.3                                                                             H      H  OCH.sub.3                                                                         OCH.sub.3                                                                           CH                              0 S  H  H          CH.sub.3                                                                             H      H  CH.sub.3                                                                          CH.sub.3                                                                            N                               0 S  H  H          CH.sub.3                                                                             H      H  CH.sub.3                                                                          OCH.sub.3                                                                           N                               0 S  H  H          CH.sub.3                                                                             H      H  OCH.sub.3                                                                         OCH.sub.3                                                                           N                               0 SO.sub.2                                                                         H  H          CH.sub.3                                                                             H      H  CH.sub.3                                                                          CH.sub.3                                                                            CH                              0 SO.sub.2                                                                         H  H          CH.sub.3                                                                             H      H  CH.sub.3                                                                          OCH.sub.3                                                                           CH                              0 SO.sub.2                                                                         H  H          CH.sub.3                                                                             H      H  OCH.sub.3                                                                         OCH.sub.3                                                                           CH                              0 SO.sub.2                                                                         H  H          CH.sub.3                                                                             H      H  CH.sub.3                                                                          CH.sub.3                                                                            N                               0 SO.sub.2                                                                         H  H          CH.sub.3                                                                             H      H  CH.sub.3                                                                          OCH.sub.3                                                                           N                               0 SO.sub.2                                                                         H  H          CH.sub.3                                                                             H      H  OCH.sub.3                                                                         OCH.sub.3                                                                           N                               0 O  H  H          CH.sub.3                                                                             CH.sub.3                                                                             H  CH.sub.3                                                                          CH.sub.3                                                                            CH                              0 O  H  H          CH.sub.3                                                                             CH.sub.3                                                                             H  CH.sub.3                                                                          OCH.sub.3                                                                           CH                              0 O  H  H          CH.sub.3                                                                             CH.sub.3                                                                             H  OCH.sub.3                                                                         OCH.sub.3                                                                           CH                              0 O  H  H          CH.sub.3                                                                             CH.sub.3                                                                             H  CH.sub.3                                                                          CH.sub.3                                                                            N                               0 O  H  H          CH.sub.3                                                                             CH.sub.3                                                                             H  CH.sub.3                                                                          OCH.sub.3                                                                           N                               0 O  H  H          CH.sub.3                                                                             CH.sub.3                                                                             H  OCH.sub.3                                                                         OCH.sub.3                                                                           N                               0 S  H  H          CH.sub.3                                                                             CH.sub.3                                                                             H  CH.sub.3                                                                          CH.sub.3                                                                            CH                              0 S  H  H          CH.sub.3                                                                             CH.sub.3                                                                             H  CH.sub.3                                                                          OCH.sub.3                                                                           CH                              0 S  H  H          CH.sub.3                                                                             CH.sub.3                                                                             H  OCH.sub.3                                                                         OCH.sub.3                                                                           CH                              0 S  H  H          CH.sub.3                                                                             CH.sub.3                                                                             H  CH.sub.3                                                                          CH.sub.3                                                                            N                               0 S  H  H          CH.sub.3                                                                             CH.sub.3                                                                             H  CH.sub.3                                                                          OCH.sub.3                                                                           N                               0 S  H  H          CH.sub.3                                                                             CH.sub.3                                                                             H  OCH.sub.3                                                                         OCH.sub.3                                                                           N                               0 SO.sub.2                                                                         H  H          CH.sub.3                                                                             CH.sub.3                                                                             H  CH.sub.3                                                                          CH.sub.3                                                                            CH                              0 SO.sub.2                                                                         H  H          CH.sub.3                                                                             CH.sub.3                                                                             H  CH.sub.3                                                                          OCH.sub.3                                                                           CH                              0 SO.sub.2                                                                         H  H          CH.sub.3                                                                             CH.sub.3                                                                             H  OCH.sub.3                                                                         OCH.sub.3                                                                           CH                              0 SO.sub.2                                                                         H  H          CH.sub.3                                                                             CH.sub.3                                                                             H  CH.sub.3                                                                          CH.sub.3                                                                            N                               0 SO.sub.2                                                                         H  H          CH.sub.3                                                                             CH.sub.3                                                                             H  CH.sub.3                                                                          OCH.sub.3                                                                           N                               0 SO.sub.2                                                                         H  H          CH.sub.3                                                                             CH.sub.3                                                                             H  OCH.sub.3                                                                         OCH.sub.3                                                                           N                               1 O  H  H          H      H      H  CH.sub.3                                                                          CH.sub.3                                                                            CH                              1 O  H  H          H      H      H  CH.sub.3                                                                          OCH.sub.3                                                                           CH                              1 O  H  H          H      H      H  OCH.sub.3                                                                         OCH.sub.3                                                                           CH                              1 O  H  H          H      H      H  CH.sub.3                                                                          CH.sub.3                                                                            N                               1 O  H  H          H      H      H  CH.sub.3                                                                          OCH.sub.3                                                                           N                               1 O  H  H          H      H      H  OCH.sub.3                                                                         OCH.sub.3                                                                           N                               1 S  H  H          H      H      H  CH.sub.3                                                                          CH.sub.3                                                                            CH                              1 S  H  H          H      H      H  CH.sub.3                                                                          OCH.sub.3                                                                           CH                              1 S  H  H          H      H      H  OCH.sub.3                                                                         OCH.sub.3                                                                           CH                              1 S  H  H          H      H      H  CH.sub.3                                                                          CH.sub.3                                                                            N                               1 S  H  H          H      H      H  CH.sub.3                                                                          OCH.sub.3                                                                           N                               1 S  H  H          H      H      H  OCH.sub.3                                                                         OCH.sub.3                                                                           N                               1 SO.sub.2                                                                         H  H          H      H      H  CH.sub.3                                                                          CH.sub.3                                                                            CH                              1 SO.sub.2                                                                         H  H          H      H      H  CH.sub.3                                                                          OCH.sub.3                                                                           CH                              1 SO.sub.2                                                                         H  H          H      H      H  OCH.sub.3                                                                         OCH.sub.3                                                                           CH                              1 SO.sub.2                                                                         H  H          H      H      H  CH.sub.3                                                                          CH.sub.3                                                                            N                               1 SO.sub.2                                                                         H  H          H      H      H  CH.sub.3                                                                          OCH.sub.3                                                                           N                               1 SO.sub.2                                                                         H  H          H      H      H  OCH.sub.3                                                                         OCH.sub.3                                                                           N                               1 O  H  H          CH.sub.3                                                                             H      H  CH.sub.3                                                                          CH.sub.3                                                                            CH                              1 O  H  H          CH.sub.3                                                                             H      H  CH.sub.3                                                                          OCH.sub.3                                                                           CH                              1 O  H  H          CH.sub.3                                                                             H      H  OCH.sub.3                                                                         OCH.sub.3                                                                           CH                              1 O  H  H          CH.sub.3                                                                             H      H  CH.sub.3                                                                          CH.sub.3                                                                            N                               1 O  H  H          CH.sub.3                                                                             H      H  CH.sub.3                                                                          OCH.sub.3                                                                           N                               1 O  H  H          CH.sub.3                                                                             H      H  OCH.sub.3                                                                         OCH.sub.3                                                                           N                               1 S  H  H          CH.sub.3                                                                             H      H  CH.sub.3                                                                          CH.sub.3                                                                            CH                              1 S  H  H          CH.sub.3                                                                             H      H  CH.sub.3                                                                          OCH.sub.3                                                                           CH                              1 S  H  H          CH.sub.3                                                                             H      H  OCH.sub. 3                                                                        OCH.sub.3                                                                           CH                              1 S  H  H          CH.sub.3                                                                             H      H  CH.sub.3                                                                          CH.sub.3                                                                            N                               1 S  H  H          CH.sub.3                                                                             H      H  CH.sub.3                                                                          OCH.sub.3                                                                           N                               1 S  H  H          CH.sub.3                                                                             H      H  OCH.sub.3                                                                         OCH.sub.3                                                                           N                               1 SO.sub.2                                                                         H  H          CH.sub.3                                                                             H      H  CH.sub.3                                                                          CH.sub.3                                                                            CH                              1 SO.sub.2                                                                         H  H          CH.sub.3                                                                             H      H  CH.sub.3                                                                          OCH.sub.3                                                                           CH                              1 SO.sub.2                                                                         H  H          CH.sub.3                                                                             H      H  OCH.sub.3                                                                         OCH.sub.3                                                                           CH                              1 SO.sub.2                                                                         H  H          CH.sub.3                                                                             H      H  CH.sub.3                                                                          CH.sub.3                                                                            N                               1 SO.sub.2                                                                         H  H          CH.sub.3                                                                             H      H  CH.sub.3                                                                          OCH.sub.3                                                                           N                               1 SO.sub.2                                                                         H  H          CH.sub.3                                                                             H      H  OCH.sub.3                                                                         OCH.sub.3                                                                           N                               1 O  H  H          CH.sub.3                                                                             CH.sub.3                                                                             H  CH.sub.3                                                                          CH.sub.3                                                                            CH                              1 O  H  H          CH.sub.3                                                                             CH.sub.3                                                                             H  CH.sub.3                                                                          OCH.sub.3                                                                           CH                              1 O  H  H          CH.sub.3                                                                             CH.sub.3                                                                             H  OCH.sub.3                                                                         OCH.sub.3                                                                           CH                              1 O  H  H          CH.sub.3                                                                             CH.sub.3                                                                             H  CH.sub.3                                                                          CH.sub.3                                                                            N                               1 O  H  H          CH.sub.3                                                                             CH.sub.3                                                                             H  CH.sub.3                                                                          OCH.sub.3                                                                           N                               1 O  H  H          CH.sub.3                                                                             CH.sub.3                                                                             H  OCH.sub.3                                                                         OCH.sub.3                                                                           N                               1 S  H  H          CH.sub.3                                                                             CH.sub.3                                                                             H  CH.sub.3                                                                          CH.sub.3                                                                            CH                              1 S  H  H          CH.sub.3                                                                             CH.sub.3                                                                             H  CH.sub.3                                                                          OCH.sub.3                                                                           CH                              1 S  H  H          CH.sub.3                                                                             CH.sub.3                                                                             H  OCH.sub.3                                                                         OCH.sub.3                                                                           CH                              1 S  H  H          CH.sub.3                                                                             CH.sub.3                                                                             H  CH.sub.3                                                                          CH.sub.3                                                                            N                               1 S  H  H          CH.sub.3                                                                             CH.sub.3                                                                             H  CH.sub.3                                                                          OCH.sub.3                                                                           N                               1 S  H  H          CH.sub.3                                                                             CH.sub.3                                                                             H  OCH.sub.3                                                                         OCH.sub.3                                                                           N                               1 SO.sub.2                                                                         H  H          CH.sub.3                                                                             CH.sub.3                                                                             H  CH.sub.3                                                                          CH.sub.3                                                                            CH                              1 SO.sub.2                                                                         H  H          CH.sub.3                                                                             CH.sub.3                                                                             H  CH.sub.3                                                                          OCH.sub.3                                                                           CH                              1 SO.sub.2                                                                         H  H          CH.sub.3                                                                             CH.sub.3                                                                             H  OCH.sub.3                                                                         OCH.sub.3                                                                           CH                              1 SO.sub.2                                                                         H  H          CH.sub.3                                                                             CH.sub.3                                                                             H  CH.sub.3                                                                          CH.sub.3                                                                            N                               1 SO.sub.2                                                                         H  H          CH.sub.3                                                                             CH.sub.3                                                                             H  CH.sub.3                                                                          OCH.sub.3                                                                           N                               1 SO.sub.2                                                                         H  H          CH.sub.3                                                                             CH.sub.3                                                                             H  OCH.sub.3                                                                         OCH.sub.3                                                                           N                               0 SO.sub.2                                                                         CH.sub.3                                                                         H          CH.sub.3                                                                             H      H  OCH.sub.3                                                                         OCH.sub.3                                                                           N                               0 SO.sub.2                                                                         H  H          H      H      CH.sub.3                                                                         CH.sub.3                                                                          CH.sub.3                                                                            CH                              0 SO.sub.2                                                                         H  H          H      H      CH.sub.3                                                                         CH.sub.3                                                                          OCH.sub.3                                                                           CH 243-245°              0 SO.sub.2                                                                         H  H          H      H      CH.sub.3                                                                         OCH.sub.3                                                                         OCH.sub.3                                                                           CH 244-245°              0 SO.sub.2                                                                         H  H          H      H      CH.sub.3                                                                         CH.sub.3                                                                          CH.sub.3                                                                            N                               0 SO.sub.2                                                                         H  H          H      H      CH.sub.3                                                                         CH.sub.3                                                                          OCH.sub.3                                                                           N  206-209°              0 SO.sub.2                                                                         H  H          H      H      CH.sub.3                                                                         OCH.sub.3                                                                         OCH.sub.3                                                                           N  228-230°              0 O  H  OCH.sub.3  CH.sub.3                                                                             CH.sub.3                                                                             H  CH.sub.3                                                                          CH.sub.3                                                                            CH                              0 O  H  OCH.sub.3  CH.sub.3                                                                             CH.sub.3                                                                             H  CH.sub.3                                                                          OCH.sub.3                                                                           CH                              0 O  H  OCH.sub.3  CH.sub.3                                                                             CH.sub.3                                                                             H  OCH.sub.3                                                                         OCH.sub.3                                                                           CH                              0 O  H  OCH.sub.3  CH.sub.3                                                                             CH.sub.3                                                                             H  CH.sub.3                                                                          CH.sub.3                                                                            N                               0 O  H  OCH.sub.3  CH.sub.3                                                                             CH.sub.3                                                                             H  CH.sub.3                                                                          OCH.sub.3                                                                           N                               0 O  H  OCH.sub.3  CH.sub.3                                                                             CH.sub.3                                                                             H  OCH.sub.3                                                                         OCH.sub.3                                                                           N                               0 O  H  CH.sub.3   H      H      H  OCH.sub.3                                                                         OCH.sub.3                                                                           CH                              0 S  H  Cl         CH.sub.3                                                                             H      H  OCH.sub.3                                                                         OCH.sub.3                                                                           CH                              0 SO.sub.2                                                                         H  Br         H      CH.sub.3                                                                             H  OCH.sub.3                                                                         OCH.sub.3                                                                           CH                              0 O  H  CO.sub.2 CH.sub.3                                                                        CH.sub.3                                                                             H      H  CH.sub.3                                                                          OCH.sub.3                                                                           CH                              0 S  H  CO.sub.2 CH.sub.2 CH.sub.3                                                               H      CH.sub.3                                                                             H  OCH.sub.3                                                                         OCH.sub.3                                                                           CH                              0 SO.sub.2                                                                         H  CO.sub.2 CH.sub.2 CH.sub.2 CH.sub.3                                                      CH.sub.3                                                                             H      H  CH.sub.3                                                                          OCH.sub.3                                                                           N                               0 O  H  CO.sub.2 CH(CH.sub.3).sub.2                                                              H      CH.sub.3                                                                             H  OCH.sub.3                                                                         OCH.sub.3                                                                           N                               0 S  H  CO.sub.2 CH.sub.2 CHCH.sub.2                                                             CH.sub.3                                                                             H      H  CH.sub.3                                                                          OCH.sub.3                                                                           CH                              0 SO.sub.2                                                                         H  CO.sub.2 CH.sub.2 CH.sub.2 OCH.sub.3                                                     H      CH.sub.3                                                                             H  OCH.sub.3                                                                         OCH.sub.3                                                                           CH                              0 O  H  CO.sub.2 CH.sub.2 CH.sub.2 Cl                                                            CH.sub.3                                                                             H      H  CH.sub.3                                                                          OCH.sub.3                                                                           N                               0 S  H  SO.sub.2 CH.sub.3                                                                        H      CH.sub.3                                                                             H  OCH.sub.3                                                                         OCH.sub.3                                                                           N                               0 SO.sub.2                                                                         H  SO.sub.2 CH.sub.2 CH.sub.2 CH.sub.3                                                      CH.sub.3                                                                             H      H  CH.sub.3                                                                          OCH.sub.3                                                                           CH                              0 O  H  SO.sub.2 CH(CH.sub.3).sub.2                                                              H      CH.sub.3                                                                             H  OCH.sub.3                                                                         OCH.sub.3                                                                           CH                              0 S  H  OSO.sub.2 CH.sub.3                                                                       CH.sub.3                                                                             H      H  CH.sub.3                                                                          OCH.sub.3                                                                           N                               0 SO.sub.2                                                                         H  OSO.sub.2 CF.sub.3                                                                       H      CH.sub.3                                                                             H  OCH.sub.3                                                                         OCH.sub.3                                                                           N                               0 O  H  OSO.sub.2 CH(CH.sub.3).sub.2                                                             H      CH.sub.3                                                                             H  CH.sub.3                                                                          OCH.sub.3                                                                           CH                              0 SO.sub.2                                                                         H  SO.sub.2 N(CH.sub.3).sub.2                                                               CH.sub.3                                                                             H      H  OCH.sub.3                                                                         OCH.sub.3                                                                           CH                              0 SO.sub.2                                                                         H  SO.sub.2 N(CH.sub.2 CH.sub.3).sub.2                                                      H      CH.sub.3                                                                             H  CH.sub.3                                                                          OCH.sub.3                                                                           N                               0 O  H  SO.sub.2 N(CH.sub.3)CH.sub.2 CH.sub.3                                                    CH.sub.3                                                                             H      H  OCH.sub.3                                                                         OCH.sub.3                                                                           N                               0 S  H  H          CH.sub.3                                                                             CH.sub.2 CH.sub.3                                                                    H  CH.sub.3                                                                          OCH.sub.3                                                                           CH                              0 SO.sub.2                                                                         H  H          H      CH.sub.2 CH.sub.2 CH.sub.3                                                           H  OCH.sub.3                                                                         OCH.sub.3                                                                           CH                              0 O  H  H          H      CH(CH.sub.3).sub.2                                                                   H  CH.sub.3                                                                          OCH.sub.3                                                                           N                               0 S  H  H          CH.sub.2 CH.sub.3                                                                    H      H  OCH.sub.3                                                                         OCH.sub.3                                                                           N                               0 SO.sub.2                                                                         H  H          CH.sub.2 CH.sub.2 CH.sub.3                                                           H      H  CH.sub.3                                                                          OCH.sub.3                                                                           CH                              0 O  H  H          CH(CH.sub.3).sub.2                                                                   H      H  OCH.sub.3                                                                         OCH.sub.3                                                                           CH                              0 S  H  H          H      CH.sub.3                                                                             H  Cl  OCH.sub.3                                                                           CH                              0 SO.sub.2                                                                         H  H          CH.sub.3                                                                             H      H  CH.sub.3                                                                          NH.sub.2                                                                            CH                              0 O  H  H          H      CH.sub.3                                                                             H  CH.sub.3                                                                          NHCH.sub.3                                                                          CH                              0 S  H  H          CH.sub.3                                                                             H      H  CH.sub.3                                                                          N(CH.sub.3).sub.2                                                                   CH                              0 SO.sub.2                                                                         H  H          H      CH.sub.3                                                                             H  CH.sub.3                                                                          OC.sub.2 H.sub.5                                                                    CH                              0 O  H  H          CH.sub.3                                                                             H      H  CH.sub.3                                                                          OCH.sub.2 CH.sub.3                                                                  N                               0 S  H  H          H      CH.sub.3                                                                             H  OCH.sub.3                                                                         CH.sub.2 OCH.sub.3                                                                  CH                              __________________________________________________________________________

                  TABLE Ib                                                        ______________________________________                                         ##STR32##                                                                    n   Q      R R.sub.1   R.sub.2                                                                            R.sub.3                                                                            R.sub.4                                                                            X'      G                               ______________________________________                                        0   SO.sub.2                                                                             H H         H    H    H    CH.sub.3                                                                              CH.sub.2                        0   SO.sub.2                                                                             H H         H    H    H    OCH.sub.3                                                                             CH.sub.2                        0   SO.sub.2                                                                             H H         H    H    H    OCH.sub.2 CH.sub.3                                                                    CH.sub.2                        0   SO.sub.2                                                                             H H         H    H    H    CH.sub.3                                                                              O                               0   SO.sub.2                                                                             H H         H    H    H    OCH.sub.3                                                                             O                               0   SO.sub.2                                                                             H H         H    H    H    OCH.sub.2 CH.sub.3                                                                    O                               0   SO.sub.2                                                                             H H         H    H    CH.sub.3                                                                           OCH.sub.3                                                                             O                               0   O      H H         H    CH.sub.3                                                                           H    OCH.sub.3                                                                             O                               0   S      H H         CH.sub.3                                                                           H    H    OCH.sub.3                                                                             O                               0   SO.sub.2                                                                             H H         H    CH.sub.3                                                                           H    OCH.sub.3                                                                             O                               0   S      H CH.sub.3  CH.sub.3                                                                           H    H    OCH.sub.3                                                                             O                               0   SO.sub.2                                                                             H OCH.sub.3 CH.sub.3                                                                           H    H    OCH.sub.3                                                                             O                               0   S      H Cl        CH.sub.3                                                                           H    H    OCH.sub.3                                                                             O                               0   SO.sub.2                                                                             H Br        CH.sub.3                                                                           H    H    OCH.sub.3                                                                             O                               0   S      H CO.sub.2 CH.sub.3                                                                       CH.sub.3                                                                           H    H    OCH.sub.3                                                                             O                               0   SO.sub.2                                                                             H SO.sub.2 CH.sub.3                                                                       CH.sub.3                                                                           H    H    OCH.sub.3                                                                             O                               0   S      H OSO.sub.2 CH.sub.3                                                                      CH.sub.3                                                                           H    H    OCH.sub.3                                                                             O                               0   SO.sub.2                                                                             H SO.sub.2 N(CH.sub.3).sub.2                                                              CH.sub.3                                                                           H    H    OCH.sub.3                                                                             O                               1   SO.sub.2                                                                             H H         H    H    H    OCH.sub.3                                                                             O                               ______________________________________                                    

                  TABLE Ic                                                        ______________________________________                                         ##STR33##                                                                    n   Q      R     R.sub.1   R.sub.2                                                                            R.sub.3                                                                            R.sub.4                                                                            X'                                  ______________________________________                                        0   SO.sub.2                                                                             H     H         H    H    H    CH.sub.3                            0   SO.sub.2                                                                             H     H         H    H    H    OCH.sub.3                           0   SO.sub.2                                                                             H     H         H    H    H    OCH.sub.2 CH.sub.3                  0   SO.sub.2                                                                             H     H         H    H    CH.sub.3                                                                           OCH.sub.3                           0   O      H     H         H    CH.sub.3                                                                           H    OCH.sub.3                           0   S      H     H         CH.sub.3                                                                           H    H    OCH.sub.3                           0   SO.sub.2                                                                             H     H         H    CH.sub.3                                                                           H    OCH.sub.3                           0   S      H     CH.sub.3  CH.sub.3                                                                           H    H    OCH.sub.3                           0   SO.sub.2                                                                             H     OCH.sub.3 CH.sub.3                                                                           H    H    OCH.sub.3                           0   S      H     Cl        CH.sub.3                                                                           H    H    OCH.sub.3                           0   SO.sub.2                                                                             H     Br        CH.sub.3                                                                           H    H    OCH.sub.3                           0   S      H     CO.sub.2 CH.sub.3                                                                       CH.sub.3                                                                           H    H    OCH.sub.3                           0   SO.sub.2                                                                             H     SO.sub.2 CH.sub.3                                                                       CH.sub.3                                                                           H    H    OCH.sub.3                           0   S      H     OSO.sub.2 CH.sub.3                                                                      CH.sub.3                                                                           H    H    OCH.sub.3                           0   SO.sub.2                                                                             H     SO.sub.2 N(CH.sub.3).sub.2                                                              CH.sub.3                                                                           H    H    OCH.sub.3                           1   SO.sub.2                                                                             H     H         H    H    H    OCH.sub.3                           ______________________________________                                    

                  TABLE Id                                                        ______________________________________                                         ##STR34##                                                                    n   Q      R     R.sub.1   R.sub.2                                                                            R.sub.3                                                                            R.sub.4                                                                            X'                                  ______________________________________                                        0   SO.sub.2                                                                             H     H         H    H    H    CH.sub.3                            0   SO.sub.2                                                                             H     H         H    H    H    OCH.sub.3                           0   SO.sub.2                                                                             H     H         H    H    H    OCH.sub.2 CH.sub.3                  0   SO.sub.2                                                                             H     H         H    H    CH.sub.3                                                                           OCH.sub.3                           0   O      H     H         H    CH.sub.3                                                                           H    OCH.sub.3                           0   S      H     H         CH.sub.3                                                                           H    H    OCH.sub.3                           0   SO.sub.2                                                                             H     H         H    CH.sub.3                                                                           H    OCH.sub.3                           0   S      H     CH.sub. 3 CH.sub.3                                                                           H    H    OCH.sub.3                           0   SO.sub.2                                                                             H     OCH.sub.3 CH.sub.3                                                                           H    H    OCH.sub.3                           0   S      H     Cl        CH.sub.3                                                                           H    H    OCH.sub.3                           0   SO.sub.2                                                                             H     Br        CH.sub.3                                                                           H    H    OCH.sub.3                           0   S      H     CO.sub.2 CH.sub.3                                                                       CH.sub.3                                                                           H    H    OCH.sub.3                           0   SO.sub.2                                                                             H     SO.sub.2 CH.sub.3                                                                       CH.sub.3                                                                           H    H    OCH.sub.3                           0   S      H     OSO.sub.2 CH.sub.3                                                                      CH.sub.3                                                                           H    H    OCH.sub.3                           0   SO.sub.2                                                                             H     SO.sub.2 N(CH.sub.3).sub.2                                                              CH.sub.3                                                                           H    H    OCH.sub.3                           1   SO.sub.2                                                                             H     H         H    H    H    OCH.sub.3                           ______________________________________                                    

                                      TABLE IIa                                   __________________________________________________________________________     ##STR35##                                                                    n Q  R  R.sub.1    R.sub.2                                                                              R.sub.3                                                                              R.sub.4                                                                           X  Y     Z  m.p. (°)              __________________________________________________________________________    0 O  H  H          H      H      H  CH.sub.3                                                                          CH.sub.3                                                                            CH                              0 O  H  H          H      H      H  CH.sub.3                                                                          OCH.sub.3                                                                           CH                              0 O  H  H          H      H      H  OCH.sub.3                                                                         OCH.sub.3                                                                           CH                              0 O  H  H          H      H      H  CH.sub.3                                                                          CH.sub.3                                                                            N                               0 O  H  H          H      H      H  CH.sub.3                                                                          OCH.sub.3                                                                           N                               0 O  H  H          H      H      H  OCH.sub.3                                                                         OCH.sub.3                                                                           N                               0 S  H  H          H      H      H  CH.sub.3                                                                          CH.sub.3                                                                            CH                              0 S  H  H          H      H      H  CH.sub.3                                                                          OCH.sub.3                                                                           CH                              0 S  H  H          H      H      H  OCH.sub.3                                                                         OCH.sub.3                                                                           CH                              0 S  H  H          H      H      H  CH.sub.3                                                                          CH.sub.3                                                                            N                               0 S  H  H          H      H      H  CH.sub.3                                                                          OCH.sub.3                                                                           N                               0 S  H  H          H      H      H  OCH.sub.3                                                                         OCH.sub.3                                                                           N                               0 SO.sub.2                                                                         H  H          H      H      H  CH.sub.3                                                                          CH.sub.3                                                                            CH                              0 SO.sub.2                                                                         H  H          H      H      H  CH.sub.3                                                                          OCH.sub.3                                                                           CH                              0 SO.sub.2                                                                         H  H          H      H      H  OCH.sub.3                                                                         OCH.sub.3                                                                           CH                              0 SO.sub.2                                                                         H  H          H      H      H  CH.sub.3                                                                          CH.sub.3                                                                            N                               0 SO.sub.2                                                                         H  H          H      H      H  CH.sub.3                                                                          OCH.sub.3                                                                           N                               0 SO.sub.2                                                                         H  H          H      H      H  OCH.sub.3                                                                         OCH.sub.3                                                                           N                               0 O  H  H          CH.sub.3                                                                             H      H  CH.sub.3                                                                          CH.sub.3                                                                            CH                              0 O  H  H          CH.sub.3                                                                             H      H  CH.sub.3                                                                          OCH.sub.3                                                                           CH                              0 O  H  H          CH.sub.3                                                                             H      H  OCH.sub.3                                                                         OCH.sub.3                                                                           CH                              0 O  H  H          CH.sub. 3                                                                            H      H  CH.sub.3                                                                          CH.sub.3                                                                            N                               0 O  H  H          CH.sub.3                                                                             H      H  CH.sub.3                                                                          OCH.sub.3                                                                           N                               0 O  H  H          CH.sub.3                                                                             H      H  OCH.sub.3                                                                         OCH.sub.3                                                                           N                               0 S  H  H          CH.sub.3                                                                             H      H  CH.sub.3                                                                          CH.sub.3                                                                            CH                              0 S  H  H          CH.sub.3                                                                             H      H  CH.sub.3                                                                          OCH.sub.3                                                                           CH                              0 S  H  H          CH.sub.3                                                                             H      H  OCH.sub.3                                                                         OCH.sub.3                                                                           CH                              0 S  H  H          CH.sub.3                                                                             H      H  CH.sub.3                                                                          CH.sub.3                                                                            N                               0 S  H  H          CH.sub.3                                                                             H      H  CH.sub.3                                                                          OCH.sub.3                                                                           N                               0 S  H  H          CH.sub.3                                                                             H      H  OCH.sub.3                                                                         OCH.sub.3                                                                           N                               0 SO.sub.2                                                                         H  H          CH.sub.3                                                                             H      H  CH.sub.3                                                                          CH.sub.3                                                                            CH                              0 SO.sub.2                                                                         H  H          CH.sub.3                                                                             H      H  CH.sub.3                                                                          OCH.sub.3                                                                           CH                              0 SO.sub.2                                                                         H  H          CH.sub.3                                                                             H      H  OCH.sub.3                                                                         OCH.sub.3                                                                           CH                              0 SO.sub.2                                                                         H  H          CH.sub.3                                                                             H      H  CH.sub.3                                                                          CH.sub.3                                                                            N                               0 SO.sub.2                                                                         H  H          CH.sub.3                                                                             H      H  CH.sub.3                                                                          OCH.sub.3                                                                           N                               0 SO.sub.2                                                                         H  H          CH.sub.3                                                                             H      H  OCH.sub.3                                                                         OCH.sub.3                                                                           N                               0 O  H  H          CH.sub.3                                                                             CH.sub.3                                                                             H  CH.sub.3                                                                          CH.sub.3                                                                            CH                              0 O  H  H          CH.sub.3                                                                             CH.sub.3                                                                             H  CH.sub.3                                                                          OCH.sub.3                                                                           CH                              0 O  H  H          CH.sub.3                                                                             CH.sub.3                                                                             H  OCH.sub.3                                                                         OCH.sub.3                                                                           CH                              0 O  H  H          CH.sub.3                                                                             CH.sub.3                                                                             H  CH.sub.3                                                                          CH.sub.3                                                                            N                               0 O  H  H          CH.sub.3                                                                             CH.sub.3                                                                             H  CH.sub.3                                                                          OCH.sub.3                                                                           N                               0 O  H  H          CH.sub.3                                                                             CH.sub.3                                                                             H  OCH.sub.3                                                                         OCH.sub.3                                                                           N                               0 S  H  H          CH.sub.3                                                                             CH.sub.3                                                                             H  CH.sub.3                                                                          CH.sub.3                                                                            CH                              0 S  H  H          CH.sub.3                                                                             CH.sub.3                                                                             H  CH.sub.3                                                                          OCH.sub.3                                                                           CH                              0 S  H  H          CH.sub.3                                                                             CH.sub.3                                                                             H  OCH.sub.3                                                                         OCH.sub.3                                                                           CH                              0 S  H  H          CH.sub.3                                                                             CH.sub.3                                                                             H  CH.sub.3                                                                          CH.sub.3                                                                            N                               0 S  H  H          CH.sub.3                                                                             CH.sub.3                                                                             H  CH.sub.3                                                                          OCH.sub.3                                                                           N                               0 S  H  H          CH.sub.3                                                                             CH.sub.3                                                                             H  OCH.sub.3                                                                         OCH.sub.3                                                                           N                               0 SO.sub.2                                                                         H  H          CH.sub.3                                                                             CH.sub.3                                                                             H  CH.sub.3                                                                          CH.sub.3                                                                            CH                              0 SO.sub.2                                                                         H  H          CH.sub.3                                                                             CH.sub.3                                                                             H  CH.sub.3                                                                          OCH.sub.3                                                                           CH                              0 SO.sub.2                                                                         H  H          CH.sub. 3                                                                            CH.sub.3                                                                             H  OCH.sub.3                                                                         OCH.sub.3                                                                           CH                              0 SO.sub.2                                                                         H  H          CH.sub.3                                                                             CH.sub.3                                                                             H  CH.sub.3                                                                          CH.sub.3                                                                            N                               0 SO.sub.2                                                                         H  H          CH.sub.3                                                                             CH.sub.3                                                                             H  CH.sub.3                                                                          OCH.sub.3                                                                           N                               0 SO.sub.2                                                                         H  H          CH.sub.3                                                                             CH.sub.3                                                                             H  OCH.sub.3                                                                         OCH.sub.3                                                                           N                               1 O  H  H          H      H      H  CH.sub.3                                                                          CH.sub.3                                                                            CH                              1 O  H  H          H      H      H  CH.sub.3                                                                          OCH.sub.3                                                                           CH                              1 O  H  H          H      H      H  OCH.sub.3                                                                         OCH.sub.3                                                                           CH                              1 O  H  H          H      H      H  CH.sub.3                                                                          CH.sub.3                                                                            N                               1 O  H  H          H      H      H  CH.sub.3                                                                          OCH.sub.3                                                                           N                               1 O  H  H          H      H      H  OCH.sub.3                                                                         OCH.sub.3                                                                           N                               1 S  H  H          H      H      H  CH.sub.3                                                                          CH.sub.3                                                                            CH                              1 S  H  H          H      H      H  CH.sub.3                                                                          OCH.sub.3                                                                           CH                              1 S  H  H          H      H      H  OCH.sub.3                                                                         OCH.sub.3                                                                           CH                              1 S  H  H          H      H      H  CH.sub.3                                                                          CH.sub.3                                                                            N                               1 S  H  H          H      H      H  CH.sub.3                                                                          OCH.sub.3                                                                           N                               1 S  H  H          H      H      H  OCH.sub.3                                                                         OCH.sub.3                                                                           N                               1 SO.sub. 2                                                                        H  H          H      H      H  CH.sub.3                                                                          CH.sub.3                                                                            CH                              1 SO.sub.2                                                                         H  H          H      H      H  CH.sub.3                                                                          OCH.sub.3                                                                           CH                              1 SO.sub.2                                                                         H  H          H      H      H  OCH.sub.3                                                                         OCH.sub.3                                                                           CH                              1 SO.sub.2                                                                         H  H          H      H      H  CH.sub.3                                                                          CH.sub.3                                                                            N                               1 SO.sub.2                                                                         H  H          H      H      H  CH.sub.3                                                                          OCH.sub.3                                                                           N                               1 SO.sub.2                                                                         H  H          H      H      H  OCH.sub.3                                                                         OCH.sub.3                                                                           N                               1 O  H  H          CH.sub.3                                                                             H      H  CH.sub.3                                                                          CH.sub.3                                                                            CH                              1 O  H  H          CH.sub.3                                                                             H      H  CH.sub.3                                                                          OCH.sub.3                                                                           CH                              1 O  H  H          CH.sub.3                                                                             H      H  OCH.sub.3                                                                         OCH.sub.3                                                                           CH                              1 O  H  H          CH.sub.3                                                                             H      H  CH.sub.3                                                                          CH.sub.3                                                                            N                               1 O  H  H          CH.sub.3                                                                             H      H  CH.sub.3                                                                          OCH.sub.3                                                                           N                               1 O  H  H          CH.sub.3                                                                             H      H  OCH.sub.3                                                                         OCH.sub.3                                                                           N                               1 S  H  H          CH.sub.3                                                                             H      H  CH.sub.3                                                                          CH.sub.3                                                                            CH                              1 S  H  H          CH.sub.3                                                                             H      H  CH.sub.3                                                                          OCH.sub.3                                                                           CH                              1 S  H  H          CH.sub.3                                                                             H      H  OCH.sub.3                                                                         OCH.sub.3                                                                           CH                              1 S  H  H          CH.sub.3                                                                             H      H  CH.sub.3                                                                          CH.sub.3                                                                            N                               1 S  H  H          CH.sub.3                                                                             H      H  CH.sub.3                                                                          OCH.sub.3                                                                           N                               1 S  H  H          CH.sub.3                                                                             H      H  OCH.sub.3                                                                         OCH.sub.3                                                                           N                               1 SO.sub.2                                                                         H  H          CH.sub.3                                                                             H      H  CH.sub.3                                                                          CH.sub.3                                                                            CH                              1 SO.sub.2                                                                         H  H          CH.sub.3                                                                             H      H  CH.sub.3                                                                          OCH.sub.3                                                                           CH                              1 SO.sub.2                                                                         H  H          CH.sub.3                                                                             H      H  OCH.sub.3                                                                         OCH.sub.3                                                                           CH                              1 SO.sub.2                                                                         H  H          CH.sub.3                                                                             H      H  CH.sub.3                                                                          CH.sub.3                                                                            N                               1 SO.sub.2                                                                         H  H          CH.sub.3                                                                             H      H  CH.sub.3                                                                          OCH.sub.3                                                                           N                               1 SO.sub.2                                                                         H  H          CH.sub.3                                                                             H      H  OCH.sub.3                                                                         OCH.sub.3                                                                           N                               1 O  H  H          CH.sub.3                                                                             CH.sub.3                                                                             H  CH.sub.3                                                                          CH.sub.3                                                                            CH                              1 O  H  H          CH.sub.3                                                                             CH.sub.3                                                                             H  CH.sub.3                                                                          OCH.sub.3                                                                           CH                              1 O  H  H          CH.sub.3                                                                             CH.sub.3                                                                             H  OCH.sub.3                                                                         OCH.sub.3                                                                           CH                              1 O  H  H          CH.sub.3                                                                             CH.sub.3                                                                             H  CH.sub.3                                                                          CH.sub.3                                                                            N                               1 O  H  H          CH.sub.3                                                                             CH.sub.3                                                                             H  CH.sub.3                                                                          OCH.sub.3                                                                           N                               1 O  H  H          CH.sub.3                                                                             CH.sub.3                                                                             H  OCH.sub.3                                                                         OCH.sub.3                                                                           N                               1 S  H  H          CH.sub.3                                                                             CH.sub.3                                                                             H  CH.sub.3                                                                          CH.sub.3                                                                            CH                              1 S  H  H          CH.sub.3                                                                             CH.sub.3                                                                             H  CH.sub.3                                                                          OCH.sub.3                                                                           CH                              1 S  H  H          CH.sub.3                                                                             CH.sub.3                                                                             H  OCH.sub.3                                                                         OCH.sub.3                                                                           CH                              1 S  H  H          CH.sub.3                                                                             CH.sub.3                                                                             H  CH.sub.3                                                                          CH.sub.3                                                                            N                               1 S  H  H          CH.sub.3                                                                             CH.sub.3                                                                             H  CH.sub.3                                                                          OCH.sub.3                                                                           N                               1 S  H  H          CH.sub.3                                                                             CH.sub.3                                                                             H  OCH.sub.3                                                                         OCH.sub.3                                                                           N                               1 SO.sub.2                                                                         H  H          CH.sub.3                                                                             CH.sub.3                                                                             H  CH.sub.3                                                                          CH.sub.3                                                                            CH                              1 SO.sub.2                                                                         H  H          CH.sub.3                                                                             CH.sub.3                                                                             H  CH.sub.3                                                                          OCH.sub.3                                                                           CH                              1 SO.sub.2                                                                         H  H          CH.sub.3                                                                             CH.sub.3                                                                             H  OCH.sub.3                                                                         OCH.sub.3                                                                           CH                              1 SO.sub.2                                                                         H  H          CH.sub.3                                                                             CH.sub.3                                                                             H  CH.sub.3                                                                          CH.sub.3                                                                            N                               1 SO.sub.2                                                                         H  H          CH.sub.3                                                                             CH.sub.3                                                                             H  CH.sub.3                                                                          OCH.sub.3                                                                           N                               1 SO.sub.2                                                                         H  H          CH.sub.3                                                                             CH.sub.3                                                                             H  OCH.sub.3                                                                         OCH.sub.3                                                                           N                               0 SO.sub.2                                                                         CH.sub.3                                                                         H          CH.sub.3                                                                             H      H  OCH.sub.3                                                                         OCH.sub.3                                                                           N                               0 SO.sub.2                                                                         H  H          H      H      CH.sub.3                                                                         CH.sub.3                                                                          CH.sub.3                                                                            CH                              0 SO.sub.2                                                                         H  H          H      H      CH.sub.3                                                                         CH.sub.3                                                                          OCH.sub.3                                                                           CH                              0 SO.sub.2                                                                         H  H          H      H      CH.sub.3                                                                         OCH.sub.3                                                                         OCH.sub.3                                                                           CH                              0 SO.sub.2                                                                         H  H          H      H      CH.sub.3                                                                         CH.sub.3                                                                          CH.sub.3                                                                            N                               0 SO.sub.2                                                                         H  H          H      H      CH.sub.3                                                                         CH.sub.3                                                                          OCH.sub.3                                                                           N                               0 SO.sub.2                                                                         H  H          H      H      CH.sub.3                                                                         OCH.sub.3                                                                         OCH.sub.3                                                                           N                               0 O  H  OCH.sub.3  CH.sub.3                                                                             CH.sub.3                                                                             H  CH.sub.3                                                                          CH.sub.3                                                                            CH                              0 O  H  OCH.sub.3  CH.sub.3                                                                             CH.sub.3                                                                             H  CH.sub.3                                                                          OCH.sub.3                                                                           CH                              0 O  H  OCH.sub.3  CH.sub.3                                                                             CH.sub.3                                                                             H  OCH.sub.3                                                                         OCH.sub.3                                                                           CH                              0 O  H  OCH.sub.3  CH.sub.3                                                                             CH.sub.3                                                                             H  CH.sub.3                                                                          CH.sub.3                                                                            N                               0 O  H  OCH.sub.3  CH.sub.3                                                                             CH.sub.3                                                                             H  CH.sub.3                                                                          OCH.sub.3                                                                           N                               0 O  H  OCH.sub.3  CH.sub.3                                                                             CH.sub.3                                                                             H  OCH.sub.3                                                                         OCH.sub.3                                                                           N                               0 O  H  CH.sub.3   H      H      H  OCH.sub.3                                                                         OCH.sub.3                                                                           CH                              0 S  H  Cl         CH.sub.3                                                                             H      H  OCH.sub.3                                                                         OCH.sub.3                                                                           CH                              0 SO.sub.2                                                                         H  Br         H      CH.sub.3                                                                             H  OCH.sub.3                                                                         OCH.sub.3                                                                           CH                              0 O  H  CO.sub.2 CH.sub.3                                                                        CH.sub.3                                                                             H      H  CH.sub.3                                                                          OCH.sub.3                                                                           CH                              0 S  H  CO.sub.2 CH.sub.2 CH.sub.3                                                               H      CH.sub.3                                                                             H  OCH.sub.3                                                                         OCH.sub.3                                                                           CH                              0 SO.sub.2                                                                         H  CO.sub.2 CH.sub.2 CH.sub.2 CH.sub.3                                                      CH.sub.3                                                                             H      H  CH.sub.3                                                                          OCH.sub.3                                                                           N                               0 O  H  CO.sub.2 CH(CH.sub.3).sub.2                                                              H      CH.sub.3                                                                             H  OCH.sub.3                                                                         OCH.sub.3                                                                           N                               0 S  H  CO.sub.2 CH.sub.2 CHCH.sub.2                                                             CH.sub.3                                                                             H      H  CH.sub.3                                                                          OCH.sub.3                                                                           CH                              0 SO.sub.2                                                                         H  CO.sub.2 CH.sub.2 CH.sub.2 OCH.sub.3                                                     H      CH.sub.3                                                                             H  OCH.sub.3                                                                         OCH.sub.3                                                                           CH                              0 O  H  CO.sub.2 CH.sub.2 CH.sub.2 Cl                                                            CH.sub.3                                                                             H      H  CH.sub.3                                                                          OCH.sub.3                                                                           N                               0 S  H  SO.sub.2 CH.sub.3                                                                        H      CH.sub.3                                                                             H  OCH.sub.3                                                                         OCH.sub.3                                                                           N                               0 SO.sub.2                                                                         H  SO.sub.2 CH.sub.2 CH.sub.2 CH.sub.3                                                      CH.sub.3                                                                             H      H  CH.sub.3                                                                          OCH.sub.3                                                                           CH                              0 O  H  SO.sub.2 CH(CH.sub.3).sub.2                                                              H      CH.sub.3                                                                             H  OCH.sub.3                                                                         OCH.sub.3                                                                           CH                              0 S  H  OSO.sub.2 CH.sub.3                                                                       CH.sub.3                                                                             H      H  CH.sub.3                                                                          OCH.sub.3                                                                           N                               0 SO.sub.2                                                                         H  OSO.sub.2 CF.sub.3                                                                       H      CH.sub.3                                                                             H  OCH.sub.3                                                                         OCH.sub.3                                                                           N                               0 O  H  OSO.sub.2 CH(CH.sub.3).sub.2                                                             H      CH.sub.3                                                                             H  CH.sub.3                                                                          OCH.sub.3                                                                           CH                              0 SO.sub.2                                                                         H  SO.sub.2 N(CH.sub.3).sub.2                                                               CH.sub.3                                                                             H      H  OCH.sub.3                                                                         OCH.sub.3                                                                           CH                              0 SO.sub.2                                                                         H  SO.sub.2 N(CH.sub.2 CH.sub.3).sub.2                                                      H      CH.sub.3                                                                             H  CH.sub.3                                                                          OCH.sub.3                                                                           N                               0 O  H  SO.sub.2 N(CH.sub.3)CH.sub.2 CH.sub.3                                                    CH.sub.3                                                                             H      H  OCH.sub.3                                                                         OCH.sub.3                                                                           N                               0 S  H  H          CH.sub.3                                                                             CH.sub.2 CH.sub.3                                                                    H  CH.sub.3                                                                          OCH.sub.3                                                                           CH                              0 SO.sub.2                                                                         H  H          H      CH.sub.2 CH.sub.2 CH.sub.3                                                           H  OCH.sub.3                                                                         OCH.sub.3                                                                           CH                              0 O  H  H          H      CH(CH.sub.3).sub.2                                                                   H  CH.sub.3                                                                          OCH.sub.3                                                                           N                               0 S  H  H          CH.sub.2 CH.sub.3                                                                    H      H  OCH.sub.3                                                                         OCH.sub.3                                                                           N                               0 SO.sub.2                                                                         H  H          CH.sub.2 CH.sub.2 CH.sub.3                                                           H      H  CH.sub.3                                                                          OCH.sub.3                                                                           CH                              0 O  H  H          CH(CH.sub.3).sub.2                                                                   H      H  OCH.sub.3                                                                         OCH.sub.3                                                                           CH                              0 S  H  H          H      CH.sub.3                                                                             H  Cl  OCH.sub.3                                                                           CH                              0 SO.sub.2                                                                         H  H          CH.sub.3                                                                             H      H  CH.sub.3                                                                          NH.sub.2                                                                            CH                              0 O  H  H          H      CH.sub.3                                                                             H  CH.sub.3                                                                          NHCH.sub.3                                                                          CH                              0 S  H  H          CH.sub.3                                                                             H      H  CH.sub.3                                                                          N(CH.sub.3).sub.2                                                                   CH                              0 SO.sub.2                                                                         H  H          H      CH.sub.3                                                                             H  CH.sub.3                                                                          OC.sub.2 H.sub.5                                                                    CH                              0 O  H  H          CH.sub.3                                                                             H      H  CH.sub.3                                                                          OCH.sub.2 CH.sub.3                                                                  N                               0 S  H  H          H      CH.sub.3                                                                             H  OCH.sub.3                                                                         CH.sub.2 OCH.sub.3                                                                  CH                              __________________________________________________________________________

                  TABLE IIb                                                       ______________________________________                                         ##STR36##                                                                    n   Q      R R.sub.1   R.sub.2                                                                            R.sub.3                                                                            R.sub.4                                                                            X'      G                               ______________________________________                                        0   SO.sub.2                                                                             H H         H    H    H    CH.sub.3                                                                              CH.sub.2                        0   SO.sub.2                                                                             H H         H    H    H    OCH.sub.3                                                                             CH.sub.2                        0   SO.sub.2                                                                             H H         H    H    H    OCH.sub.2 CH.sub.3                                                                    CH.sub.2                        0   SO.sub.2                                                                             H H         H    H    H    CH.sub.3                                                                              O                               0   SO.sub.2                                                                             H H         H    H    H    OCH.sub.3                                                                             O                               0   SO.sub.2                                                                             H H         H    H    H    OCH.sub.2 CH.sub.3                                                                    O                               0   SO.sub.2                                                                             H H         H    H    CH.sub. 3                                                                          OCH.sub.3                                                                             O                               0   O      H H         H    CH.sub.3                                                                           H    OCH.sub.3                                                                             O                               0   S      H H         CH.sub.3                                                                           H    H    OCH.sub.3                                                                             O                               0   SO.sub.2                                                                             H H         H    CH.sub.3                                                                           H    OCH.sub.3                                                                             O                               0   S      H CH.sub.3  CH.sub.3                                                                           H    H    OCH.sub.3                                                                             O                               0   SO.sub.2                                                                             H OCH.sub.3 CH.sub.3                                                                           H    H    OCH.sub.3                                                                             O                               0   S      H Cl        CH.sub.3                                                                           H    H    OCH.sub.3                                                                             O                               0   SO.sub.2                                                                             H Br        CH.sub.3                                                                           H    H    OCH.sub.3                                                                             O                               0   S      H CO.sub.2 CH.sub.3                                                                       CH.sub.3                                                                           H    H    OCH.sub.3                                                                             O                               0   SO.sub.2                                                                             H SO.sub.2 CH.sub.3                                                                       CH.sub.3                                                                           H    H    OCH.sub.3                                                                             O                               0   S      H OSO.sub.2 CH.sub.3                                                                      CH.sub.3                                                                           H    H    OCH.sub.3                                                                             O                               0   SO.sub.2                                                                             H SO.sub.2 N(CH.sub.3).sub.2                                                              CH.sub.3                                                                           H    H    OCH.sub.3                                                                             O                               1   SO.sub.2                                                                             H H         H    H    H    OCH.sub.3                                                                             O                               ______________________________________                                    

                  TABLE IIc                                                       ______________________________________                                         ##STR37##                                                                    n   Q      R     R.sub.1   R.sub.2                                                                            R.sub.3                                                                            R.sub.4                                                                            X'                                  ______________________________________                                        0   SO.sub.2                                                                             H     H         H    H    H    CH.sub.3                            0   SO.sub.2                                                                             H     H         H    H    H    OCH.sub.3                           0   SO.sub.2                                                                             H     H         H    H    H    OCH.sub.2 CH.sub.3                  0   SO.sub.2                                                                             H     H         H    H    CH.sub.3                                                                           OCH.sub.3                           0   O      H     H         H    CH.sub.3                                                                           H    OCH.sub.3                           0   S      H     H         CH.sub.3                                                                           H    H    OCH.sub.3                           0   SO.sub.2                                                                             H     H         H    CH.sub.3                                                                           H    OCH.sub.3                           0   S      H     CH.sub.3  CH.sub.3                                                                           H    H    OCH.sub.3                           0   SO.sub.2                                                                             H     OCH.sub.3 CH.sub.3                                                                           H    H    OCH.sub.3                           0   S      H     Cl        CH.sub.3                                                                           H    H    OCH.sub.3                           0   SO.sub.2                                                                             H     Br        CH.sub.3                                                                           H    H    OCH.sub.3                           0   S      H     CO.sub.2 CH.sub.3                                                                       CH.sub.3                                                                           H    H    OCH.sub.3                           0   SO.sub.2                                                                             H     SO.sub.2 CH.sub.3                                                                       CH.sub.3                                                                           H    H    OCH.sub.3                           0   S      H     OSO.sub.2 CH.sub.3                                                                      CH.sub.3                                                                           H    H    OCH.sub.3                           0   SO.sub.2                                                                             H     SO.sub.2 N(CH.sub.3).sub.2                                                              CH.sub.3                                                                           H    H    OCH.sub.3                           1   SO.sub.2                                                                             H     H         H    H    H    OCH.sub.3                           ______________________________________                                    

                  TABLE IId                                                       ______________________________________                                         ##STR38##                                                                    n   Q      R     R.sub.1   R.sub.2                                                                            R.sub.3                                                                            R.sub.4                                                                            X'                                  ______________________________________                                        0   SO.sub.2                                                                             H     H         H    H    H    CH.sub.3                            0   SO.sub.2                                                                             H     H         H    H    H    OCH.sub.3                           0   SO.sub.2                                                                             H     H         H    H    H    OCH.sub.2 CH.sub.3                  0   SO.sub.2                                                                             H     H         H    H    CH.sub.3                                                                           OCH.sub.3                           0   O      H     H         H    CH.sub.3                                                                           H    OCH.sub.3                           0   S      H     H         CH.sub.3                                                                           H    H    OCH.sub.3                           0   SO.sub.2                                                                             H     H         H    CH.sub.3                                                                           H    OCH.sub.3                           0   S      H     CH.sub. 3 CH.sub.3                                                                           H    H    OCH.sub.3                           0   SO.sub.2                                                                             H     OCH.sub.3 CH.sub.3                                                                           H    H    OCH.sub.3                           0   S      H     Cl        CH.sub.3                                                                           H    H    OCH.sub.3                           0   SO.sub.2                                                                             H     Br        CH.sub.3                                                                           H    H    OCH.sub.3                           0   S      H     CO.sub.2 CH.sub.3                                                                       CH.sub.3                                                                           H    H    OCH.sub.3                           0   SO.sub.2                                                                             H     SO.sub.2 CH.sub.3                                                                       CH.sub.3                                                                           H    H    OCH.sub.3                           0   S      H     OSO.sub.2 CH.sub.3                                                                      CH.sub.3                                                                           H    H    OCH.sub.3                           0   SO.sub.2                                                                             H     SO.sub.2 N(CH.sub.3).sub.2                                                              CH.sub.3                                                                           H    H    OCH.sub.3                           1   SO.sub.2                                                                             H     H         H    H    H    OCH.sub.3                           ______________________________________                                    

                                      TABLE IIIa                                  __________________________________________________________________________     ##STR39##                                                                    n Q  R  R.sub.1    R.sub.2                                                                              R.sub.4                                                                         X   Y     Z  m.p. (°)                      __________________________________________________________________________    0 S  H  H          H      H CH.sub.3                                                                          CH.sub.3                                                                            CH                                      0 S  H  H          H      H CH.sub.3                                                                          OCH.sub.3                                                                           CH                                      0 S  H  H          H      H OCH.sub.3                                                                         OCH.sub.3                                                                           CH                                      0 S  H  H          H      H CH.sub.3                                                                          CH.sub.3                                                                            N                                       0 S  H  H          H      H CH.sub.3                                                                          OCH.sub.3                                                                           N                                       0 S  H  H          H      H OCH.sub.3                                                                         OCH.sub.3                                                                           N                                       0 SO.sub.2                                                                         H  H          H      H CH.sub.3                                                                          CH.sub.3                                                                            CH                                      0 SO.sub. 2                                                                        H  H          H      H CH.sub.3                                                                          OCH.sub.3                                                                           CH                                      0 SO.sub.2                                                                         H  H          H      H OCH.sub.3                                                                         OCH.sub.3                                                                           CH                                      0 SO.sub.2                                                                         H  H          H      H CH.sub.3                                                                          CH.sub.3                                                                            N                                       0 SO.sub.2                                                                         H  H          H      H CH.sub.3                                                                          OCH.sub.3                                                                           N                                       0 SO.sub.2                                                                         H  H          H      H OCH.sub.3                                                                         OCH.sub.3                                                                           N                                       0 S  H  H          CH.sub.3                                                                             H CH.sub.3                                                                          CH.sub.3                                                                            CH                                      0 S  H  H          CH.sub.3                                                                             H CH.sub.3                                                                          OCH.sub.3                                                                           CH                                      0 S  H  H          CH.sub.3                                                                             H OCH.sub.3                                                                         OCH.sub.3                                                                           CH                                      0 S  H  H          CH.sub.3                                                                             H CH.sub.3                                                                          CH.sub.3                                                                            N                                       0 S  H  H          CH.sub.3                                                                             H CH.sub.3                                                                          OCH.sub.3                                                                           N                                       0 S  H  H          CH.sub.3                                                                             H OCH.sub.3                                                                         OCH.sub.3                                                                           N                                       0 SO.sub.2                                                                         H  H          CH.sub.3                                                                             H CH.sub.3                                                                          CH.sub.3                                                                            CH                                      0 SO.sub.2                                                                         H  H          CH.sub.3                                                                             H CH.sub.3                                                                          OCH.sub.3                                                                           CH                                      0 SO.sub.2                                                                         H  H          CH.sub.3                                                                             H OCH.sub.3                                                                         OCH.sub.3                                                                           CH                                      0 SO.sub.2                                                                         H  H          CH.sub.3                                                                             H CH.sub.3                                                                          CH.sub.3                                                                            N                                       0 SO.sub.2                                                                         H  H          CH.sub.3                                                                             H CH.sub.3                                                                          OCH.sub.3                                                                           N                                       0 SO.sub.2                                                                         H  H          CH.sub.3                                                                             H OCH.sub.3                                                                         OCH.sub.3                                                                           N                                       1 S  H  H          H      H CH.sub.3                                                                          CH.sub.3                                                                            CH                                      1 S  H  H          H      H CH.sub.3                                                                          OCH.sub.3                                                                           CH                                      1 S  H  H          H      H OCH.sub.3                                                                         OCH.sub.3                                                                           CH                                      1 S  H  H          H      H CH.sub.3                                                                          CH.sub.3                                                                            N                                       1 S  H  H          H      H CH.sub.3                                                                          OCH.sub.3                                                                           N                                       1 S  H  H          H      H OCH.sub.3                                                                         OCH.sub.3                                                                           N                                       1 SO.sub.2                                                                         H  H          H      H CH.sub.3                                                                          CH.sub.3                                                                            CH                                      1 SO.sub.2                                                                         H  H          H      H CH.sub.3                                                                          OCH.sub.3                                                                           CH                                      1 SO.sub.2                                                                         H  H          H      H OCH.sub.3                                                                         OCH.sub.3                                                                           CH                                      1 SO.sub.2                                                                         H  H          H      H CH.sub.3                                                                          CH.sub.3                                                                            N                                       1 SO.sub.2                                                                         H  H          H      H CH.sub.3                                                                          OCH.sub.3                                                                           N                                       1 SO.sub.2                                                                         H  H          H      H OCH.sub.3                                                                         OCH.sub.3                                                                           N                                       1 S  H  H          CH.sub.3                                                                             H CH.sub.3                                                                          CH.sub.3                                                                            CH                                      1 S  H  H          CH.sub.3                                                                             H CH.sub.3                                                                          OCH.sub.3                                                                           CH                                      1 S  H  H          CH.sub.3                                                                             H OCH.sub.3                                                                         OCH.sub.3                                                                           CH                                      1 S  H  H          CH.sub.3                                                                             H CH.sub.3                                                                          CH.sub.3                                                                            N                                       1 S  H  H          CH.sub.3                                                                             H CH.sub.3                                                                          OCH.sub.3                                                                           N                                       1 S  H  H          CH.sub.3                                                                             H OCH.sub.3                                                                         OCH.sub.3                                                                           N                                       1 SO.sub.2                                                                         H  H          CH.sub.3                                                                             H CH.sub.3                                                                          CH.sub.3                                                                            CH                                      1 SO.sub.2                                                                         H  H          CH.sub.3                                                                             H CH.sub.3                                                                          OCH.sub.3                                                                           CH                                      1 SO.sub.2                                                                         H  H          CH.sub.3                                                                             H OCH.sub.3                                                                         OCH.sub.3                                                                           CH                                      1 SO.sub.2                                                                         H  H          CH.sub.3                                                                             H CH.sub.3                                                                          CH.sub.3                                                                            N                                       1 SO.sub.2                                                                         H  H          CH.sub.3                                                                             H CH.sub.3                                                                          OCH.sub.3                                                                           N                                       1 SO.sub.2                                                                         H  H          CH.sub.3                                                                             H OCH.sub.3                                                                         OCH.sub.3                                                                           N                                       0 SO.sub.2                                                                         CH.sub.3                                                                         H          CH.sub.3                                                                             H OCH.sub.3                                                                         OCH.sub.3                                                                           N                                       0 S  H  CH.sub.3   H      H OCH.sub.3                                                                         OCH.sub.3                                                                           CH                                      0 S  H  Cl         CH.sub.3                                                                             H OCH.sub.3                                                                         OCH.sub.3                                                                           CH                                      0 SO.sub.2                                                                         H  Br         H      H OCH.sub.3                                                                         OCH.sub.3                                                                           CH                                      0 S  H  CO.sub.2 CH.sub.3                                                                        CH.sub.3                                                                             H CH.sub.3                                                                          OCH.sub.3                                                                           CH                                      0 S  H  CO.sub.2 CH.sub.2 CH.sub.3                                                               H      H OCH.sub.3                                                                         OCH.sub.3                                                                           CH                                      0 SO.sub.2                                                                         H  CO.sub.2 CH.sub.2 CH.sub.2 CH.sub.3                                                      CH.sub.3                                                                             H CH.sub.3                                                                          OCH.sub.3                                                                           N                                       0 S  H  CO.sub.2 CH(CH.sub.3).sub.2                                                              H      H OCH.sub.3                                                                         OCH.sub.3                                                                           N                                       0 S  H  CO.sub.2 CH.sub.2 CHCH.sub.2                                                             CH.sub.3                                                                             H CH.sub.3                                                                          OCH.sub.3                                                                           CH                                      0 SO.sub.2                                                                         H  CO.sub.2 CH.sub.2 CH.sub.2 OCH.sub.3                                                     H      H OCH.sub.3                                                                         OCH.sub.3                                                                           CH                                      0 S  H  CO.sub.2 CH.sub.2 CH.sub.2 Cl                                                            CH.sub.3                                                                             H CH.sub.3                                                                          OCH.sub.3                                                                           N                                       0 S  H  SO.sub.2 CH.sub.3                                                                        H      H OCH.sub.3                                                                         OCH.sub.3                                                                           N                                       0 SO.sub.2                                                                         H  SO.sub.2 CH.sub.2 CH.sub.2 CH.sub.3                                                      CH.sub.3                                                                             H CH.sub.3                                                                          OCH.sub.3                                                                           CH                                      0 S  H  SO.sub.2 CH(CH.sub.3).sub.2                                                              H      H OCH.sub.3                                                                         OCH.sub.3                                                                           CH                                      0 S  H  OSO.sub.2 CH.sub.3                                                                       CH.sub.3                                                                             H CH.sub.3                                                                          OCH.sub.3                                                                           N                                       0 SO.sub.2                                                                         H  OSO.sub.2 CF.sub.3                                                                       H      H OCH.sub.3                                                                         OCH.sub.3                                                                           N                                       0 S  H  OSO.sub.2 CH(CH.sub.3).sub.2                                                             H      H CH.sub.3                                                                          OCH.sub.3                                                                           CH                                      0 SO.sub.2                                                                         H  SO.sub.2 N(CH.sub.3).sub.2                                                               CH.sub.3                                                                             H OCH.sub.3                                                                         OCH.sub.3                                                                           CH                                      0 SO.sub.2                                                                         H  SO.sub.2 N(CH.sub.2 CH.sub.3).sub.2                                                      H      H CH.sub.3                                                                          OCH.sub.3                                                                           N                                       0 SO.sub.2                                                                         H  SO.sub.2 N(CH.sub.3)CH.sub.2 CH.sub.3                                                    CH.sub.3                                                                             H OCH.sub.3                                                                         OCH.sub.3                                                                           N                                       0 S  H  H          CH.sub.2 CH.sub.3                                                                    H OCH.sub.3                                                                         OCH.sub.3                                                                           N                                       0 SO.sub.2                                                                         H  H          CH.sub.2 CH.sub.2 CH.sub.3                                                           H CH.sub.3                                                                          OCH.sub.3                                                                           CH                                      0 S  H  H          CH(CH.sub.3).sub.2                                                                   H OCH.sub.3                                                                         OCH.sub.3                                                                           CH                                      0 S  H  H          H      H Cl  OCH.sub.3                                                                           CH                                      0 SO.sub.2                                                                         H  H          CH.sub.3                                                                             H CH.sub.3                                                                          NH.sub.2                                                                            CH                                      0 S  H  H          H      H CH.sub.3                                                                          NHCH.sub.3                                                                          CH                                      0 S  H  H          CH.sub.3                                                                             H CH.sub.3                                                                          N(CH.sub.3).sub.2                                                                   CH                                      0 SO.sub.2                                                                         H  H          H      H CH.sub.3                                                                          OC.sub.2 H.sub.5                                                                    CH                                      0 S  H  H          CH.sub.3                                                                             H CH.sub.3                                                                          OCH.sub.2 CH.sub.3                                                                  N                                       0 S  H  H          H      H OCH.sub.3                                                                         CH.sub.2 OCH.sub.3                                                                  CH                                      __________________________________________________________________________

                  TABLE IIIb                                                      ______________________________________                                         ##STR40##                                                                    n    Q      R     R.sub.1  R.sub.2                                                                            R.sub.4                                                                            X'       G                               ______________________________________                                        0    SO.sub.2                                                                             H     H        H    H    CH.sub.3 CH.sub.2                        0    SO.sub.2                                                                             H     H        H    H    OCH.sub.3                                                                              CH.sub.2                        0    SO.sub.2                                                                             H     H        H    H    OCH.sub.2 CH.sub.3                                                                     CH.sub.2                        0    SO.sub.2                                                                             H     H        H    H    CH.sub.3 0                               0    SO.sub.2                                                                             H     H        H    H    OCH.sub.3                                                                              0                               0    SO.sub.2                                                                             H     H        H    H    OCH.sub.2 CH.sub.3                                                                     0                               0    SO.sub.2                                                                             H     H        H    CH.sub.3                                                                           OCH.sub.3                                                                              0                               0    S      H     H        CH.sub.3                                                                           H    OCH.sub.3                                                                              0                               0    SO.sub.2                                                                             H     H        H    H    OCH.sub.3                                                                              0                               0    S      H     CH.sub.3 CH.sub.3                                                                           H    OCH.sub.3                                                                              0                               0    SO.sub.2                                                                             H     OCH.sub.3                                                                              CH.sub.3                                                                           H    OCH.sub.3                                                                              0                               0    S      H     Cl       CH.sub.3                                                                           H    OCH.sub.3                                                                              0                               0    SO.sub.2                                                                             H     Br       CH.sub.3                                                                           H    OCH.sub.3                                                                              0                               0    S      H     CO.sub.2 CH.sub.3                                                                      CH.sub.3                                                                           H    OCH.sub.3                                                                              0                               0    SO.sub.2                                                                             H     SO.sub.2 CH.sub.3                                                                      CH.sub.3                                                                           H    OCH.sub.3                                                                              0                               0    S      H     OSO.sub.2 CH.sub.3                                                                     CH.sub.3                                                                           H    OCH.sub.3                                                                              0                               0    SO.sub.2                                                                             H     SO.sub.2 N(CH.sub.3).sub.2                                                             CH.sub.3                                                                           H    OCH.sub.3                                                                              0                               1    SO.sub.2                                                                             H     H        H    H    OCH.sub.3                                                                              0                               ______________________________________                                    

                  TABLE IIIc                                                      ______________________________________                                         ##STR41##                                                                    n    Q      R      R.sub.1   R.sub.2                                                                             R.sub.4                                                                             X'                                   ______________________________________                                        0    SO.sub.2                                                                             H      H         H     H     CH.sub.3                             0    SO.sub.2                                                                             H      H         H     H     OCH.sub.3                            0    SO.sub.2                                                                             H      H         H     H     OCH.sub.2 CH.sub.3                   0    SO.sub.2                                                                             H      H         H     CH.sub.3                                                                            OCH.sub.3                            0    S      H      H         CH.sub.3                                                                            H     OCH.sub.3                            0    SO.sub.2                                                                             H      H         H     H     OCH.sub.3                            0    S      H      CH.sub.3  CH.sub.3                                                                            H     OCH.sub.3                            0    SO.sub.2                                                                             H      OCH.sub.3 CH.sub.3                                                                            H     OCH.sub.3                            0    S      H      Cl        CH.sub.3                                                                            H     OCH.sub.3                            0    SO.sub. 2                                                                            H      Br        CH.sub.3                                                                            H     OCH.sub.3                            0    S      H      CO.sub.2 CH.sub.3                                                                       CH.sub.3                                                                            H     OCH.sub.3                            0    SO.sub.2                                                                             H      SO.sub.2 CH.sub.3                                                                       CH.sub.3                                                                            H     OCH.sub.3                            0    S      H      OSO.sub.2 CH.sub.3                                                                      CH.sub.3                                                                            H     OCH.sub.3                            0    SO.sub.2                                                                             H      SO.sub.2 N(CH.sub.3).sub.2                                                              CH.sub.3                                                                            H     OCH.sub.3                            1    SO.sub.2                                                                             H      H         H     H     OCH.sub.3                            ______________________________________                                    

                  TABLE IIId                                                      ______________________________________                                         ##STR42##                                                                    n    Q      R      R.sub.1   R.sub.2                                                                             R.sub.4                                                                             X'                                   ______________________________________                                        0    SO.sub.2                                                                             H      H         H     H     CH.sub.3                             0    SO.sub.2                                                                             H      H         H     H     OCH.sub.3                            0    SO.sub.2                                                                             H      H         H     H     OCH.sub.2 CH.sub.3                   0    SO.sub.2                                                                             H      H         H     CH.sub.3                                                                            OCH.sub.3                            0    S      H      H         CH.sub.3                                                                            H     OCH.sub.3                            0    SO.sub.2                                                                             H      H         H     H     OCH.sub.3                            0    S      H      CH.sub.3  CH.sub.3                                                                            H     OCH.sub.3                            0    SO.sub.2                                                                             H      OCH.sub.3 CH.sub.3                                                                            H     OCH.sub.3                            0    S      H      Cl        CH.sub.3                                                                            H     OCH.sub. 3                           0    SO.sub.2                                                                             H      Br        CH.sub.3                                                                            H     OCH.sub.3                            0    S      H      CO.sub.2 CH.sub.3                                                                       CH.sub.3                                                                            H     OCH.sub.3                            0    SO.sub.2                                                                             H      SO.sub.2 CH.sub.3                                                                       CH.sub.3                                                                            H     OCH.sub.3                            0    S      H      OSO.sub.2 CH.sub.3                                                                      CH.sub.3                                                                            H     OCH.sub.3                            0    SO.sub.2                                                                             H      SO.sub.2 N(CH.sub.3).sub.2                                                              CH.sub.3                                                                            H     OCH.sub.3                            1    SO.sub.2                                                                             H      H         H     H     OCH.sub.3                            ______________________________________                                    

                  TABLE IVa                                                       ______________________________________                                         ##STR43##                                                                                                             m.p.                                 R    R.sub.1    R.sub.2    X     Y       Z(°)                          ______________________________________                                        H    H          H          CH.sub.3                                                                            CH.sub.3                                                                              CH                                   H    H          H          CH.sub.3                                                                            OCH.sub.3                                                                             CH                                   H    H          H          OCH.sub.3                                                                           OCH.sub.3                                                                             CH                                   H    H          H          CH.sub.3                                                                            CH.sub.3                                                                              N                                    H    H          H          CH.sub.3                                                                            OCH.sub.3                                                                             N                                    H    H          H          OCH.sub.3                                                                           OCH.sub.3                                                                             N                                    CH.sub.3                                                                           H          H          OCH.sub.3                                                                           OCH.sub.3                                                                             N                                    H    H          CH.sub.3   CH.sub.3                                                                            CH.sub.3                                                                              CH                                   H    H          CH.sub.3   CH.sub.3                                                                            OCH.sub.3                                                                             CH                                   H    H          CH.sub.3   OCH.sub.3                                                                           OCH.sub.3                                                                             CH                                   H    H          CH.sub.3   CH.sub.3                                                                            CH.sub. 3                                                                             N                                    H    H          CH.sub.3   CH.sub.3                                                                            OCH.sub.3                                                                             N                                    H    H          CH.sub.3   OCH.sub.3                                                                           OCH.sub.3                                                                             N                                    H    H          CH.sub.2 CH.sub.3                                                                        CH.sub.3                                                                            OCH.sub.3                                                                             CH                                   H    H          CH.sub.2 CH.sub.2 CH.sub.3                                                               OCH.sub.3                                                                           OCH.sub.3                                                                             CH                                   H    H          CH(CH.sub.3).sub.2                                                                       CH.sub.3                                                                            OCH.sub.3                                                                             CH                                   H    OCH.sub.3  H          CH.sub.3                                                                            OCH.sub.3                                                                             N                                    H    Cl         H          OCH.sub.3                                                                           OCH.sub.3                                                                             N                                    H    Br         H          CH.sub.3                                                                            OCH.sub.3                                                                             CH                                   H    CO.sub.2 CH.sub.3                                                                        H          OCH.sub.3                                                                           OCH.sub.3                                                                             CH                                   H    SO.sub.2 CH.sub.3                                                                        H          CH.sub.3                                                                            OCH.sub.3                                                                             N                                    H    OSO.sub.2 CH.sub.3                                                                       H          OCH.sub.3                                                                           OCH.sub.3                                                                             N                                    H    SO.sub.2 N(CH.sub.3).sub.2                                                               H          CH.sub.3                                                                            OCH.sub.3                                                                             CH                                   H    H          H          Cl    OCH.sub.3                                                                             CH                                   H    H          H          OCH.sub.3                                                                           OCH.sub.2 CH.sub.3                                                                    CH                                   H    H          H          OCH.sub.3                                                                           CH.sub.2 OCH.sub.3                                                                    CH                                   H    H          H          OCH.sub.3                                                                           NH.sub.2                                                                              CH                                   H    H          H          OCH.sub.3                                                                           NHCH.sub.3                                                                            CH                                   H    H          H          OCH.sub.3                                                                           N(CH.sub.3).sub.2                                                                     CH                                   ______________________________________                                    

                  TABLE IVb                                                       ______________________________________                                         ##STR44##                                                                    R       R.sub.1     R.sub.2 X'        G                                       ______________________________________                                        H       H           H       CH.sub.3  O                                       H       H           H       OCH.sub.3 O                                       H       H           H       OCH.sub.2 CH.sub.3                                                                      O                                       H       H           CH.sub.3                                                                              OCH.sub.3 O                                       CH.sub.3                                                                              H           H       OCH.sub.3 O                                       H       OCH.sub.3   H       OCH.sub.3 O                                       H       Cl          H       OCH.sub.3 O                                       H       Br          H       OCH.sub.3 O                                       H       CO.sub.2 CH.sub.3                                                                         H       OCH.sub.3 O                                       H       SO.sub.2 CH.sub.3                                                                         H       OCH.sub.3 O                                       H       OSO.sub.2 CH.sub.3                                                                        H       OCH.sub.3 O                                       H       SO.sub.2 N(CH.sub.3).sub.2                                                                H       OCH.sub.3 O                                       H       H           H       OCH.sub.3 CH.sub.2                                ______________________________________                                    

                  TABLE IVc                                                       ______________________________________                                         ##STR45##                                                                    R         R.sub.1      R.sub.2  X'                                            ______________________________________                                        H         H            H        CH.sub.3                                      H         H            H        OCH.sub.3                                     H         H            H        OCH.sub.2 CH.sub.3                            H         H            CH.sub.3 OCH.sub.3                                     CH.sub.3  H            H        OCH.sub.3                                     H         OCH.sub.3    H        OCH.sub.3                                     H         Cl           H        OCH.sub.3                                     H         Br           H        OCH.sub.3                                     H         CO.sub.2 CH.sub.3                                                                          H        OCH.sub.3                                     H         SO.sub.2 CH.sub.3                                                                          H        OCH.sub.3                                     H         OSO.sub.2 CH.sub.3                                                                         H        OCH.sub.3                                     H         SO.sub.2 N(CH.sub.3).sub.2                                                                 H        OCH.sub.3                                     ______________________________________                                    

                  TABLE IVd                                                       ______________________________________                                         ##STR46##                                                                    R         R.sub.1      R.sub.2  X'                                            ______________________________________                                        H         H            H        CH.sub.3                                      H         H            H        OCH.sub.3                                     H         H            H        OCH.sub.2 CH.sub.3                            H         H            CH.sub.3 OCH.sub.3                                     CH.sub.3  H            H        OCH.sub.3                                     H         OCH.sub.3    H        OCH.sub.3                                     H         Cl           H        OCH.sub.3                                     H         Br           H        OCH.sub.3                                     H         CO.sub.2 CH.sub.3                                                                          H        OCH.sub.3                                     H         SO.sub.2 CH.sub.3                                                                          H        OCH.sub.3                                     H         OSO.sub.2 CH.sub.3                                                                         H        OCH.sub.3                                     H         SO.sub.2 N(CH.sub.3).sub.2                                                                 H        OCH.sub.3                                     ______________________________________                                    

Formulations

Useful formulations of the compounds of Formula I can be prepared inconventional ways. They include dusts, granules, pellets, solutions,suspensions, emulsions, wettable powders, emulsifiable concentrates andthe like. Many of these may be applied directly. Sprayable formulationscan be extended in suitable media and used at spray volumes of from afew liters to several hundred liters per hectare. High strengthcompositions are primarily used as intermediates for furtherformulation. The formulations, broadly, contain about 0.1% to 99% byweight of active ingredient(s) and at least one of (a) about 0.1% to 20%surfactant(s) and (b) about 1% to 99.9% solid or liquid inertdiluent(s). More specifically, they will contain these ingredients inthe following approximate proportions:

                  TABLE V                                                         ______________________________________                                                    Active  Weight Percent*                                                       Ingredient                                                                            Diluent(s)                                                                              Surfactant(s)                                   ______________________________________                                        Wettable Powders                                                                            20-90      0-74     1-10                                        Oil Suspensions,                                                                             3-50     40-95     0-15                                        Emulsions, Solutions,                                                         (including Emulsifiable                                                       Concentrates)                                                                 Aqueous Suspension                                                                          10-50     40-84     1-20                                        Dusts          1-25     70-99     0-5                                         Granules snd Pellets                                                                        0.1-95      5-99.9  0-15                                        High Strength 90-99      0-10     0-2                                         Compositions                                                                  ______________________________________                                         *Active ingredient plus at least one of a Surfactant or a Diluent equals      100 weight percent.                                                      

Lower or higher levels of active ingredient can, of course, be presentdepending on the intended use and the physical properties of thecompound. Higher ratios of surfactant to active ingredient are sometimesdesirable, and are achieved by incorporation into the formulation or bytank mixing.

Typical solid diluents are described in Watkins, et al., "Handbook ofInsecticide Dust Diluents and Carriers", 2nd Ed., Dorland Books,Caldwell, N.J., but other solids, either mined or manufactured, may beused. The more absorptive diluents are preferred for wettable powdersand the denser ones for dusts. Typical liquid diluents and solvents aredescribed in Marsden, "Solvents Guide," 2nd Ed., Interscience, New York,1950. Solubility under 0.1% is preferred for suspension concentrates;solution concentrates are preferably stable against phase separation at0° C. "McCutcheon's Detergents and Emulsifiers Annual", MC PublishingCorp., Ridgewood, N.J., as well as Sisely and Wood, "Encyclopedia ofSurface Active Agents", Chemical Publishing Co., Inc., New York, 1964,list surfactants are recommended uses. All formulations can containminor amounts of additives for reduce foaming, caking, corrosion,microbiological growth, etc.

The methods of making such compositions are well known. Solutions areprepared by simply mixing the ingredients. Fine solid compositions aremade by blending and, usually, grinding as in a hammer or fluid energymill. Suspensions are prepared by wet milling (see, for example,Littler, U.S. Pat. No. 3,060,084). Granules and pellets may be made byspraying the active material upon preformed granular carriers or byagglomeration techniques. See J. E. Browning, "Agglomeration", ChemicalEngineering, Dec. 4, 1967, pp. 147ff. and "Perry's Chemical Engineer'sHandbook", 5th Ed., McGraw-Hill, New York, 1973, pp. 8-57ff.

For further information regarding the art of formulation, see forexample:

H. M. Loux, U.S. Pat. No. 3,235,361, Feb. 15, 1966, Col. 6, line 16through Col. 7, line 19 and Examples 10 through 41;

R. W. Luckenbaugh, U.S. Pat. No. 3,309,192, Mar. 14, 1967, Col. 5, line43 through Col. 7, line 62 and Examples 8, 12, 15, 39, 41, 52, 53, 58,132, 138-140, 162-164, 166, 167 and 169-182;

H. Gysin and E. Knusli, U.S. Pat. No. 2,891,855, June 23, 1959, Col. 3,line 66 through Col. 5, line 17 and Examples 1-4;

G. C. Klingman, "Weed Control as a Science", John Wiley & Sons, Inc.,New York, 1961, pp. 81-96; and

J. D. Fryer and S. A. Evans, "Weed Control Handbook", 5th Ed., BlackwellScientific Publications, Oxford, 1968, pp. 101-103.

In the following examples, all parts are by weight unless otherwiseindicated.

EXAMPLE 8

Wettable Powder

    ______________________________________                                        N--[(4-methoxy-6-methylpyrimidin-2-yl)aminocarbonyl]-                                                       80%                                             3,4-dihydro-2H--1-benzothiopyran-8-sulfonamide, 1,1-                          dioxide                                                                       sodium alkylnaphthalenesulfonate                                                                            2%                                              sodium ligninsulfonate        2%                                              synthetic amorphous silica    3%                                              kaolinite                     13%                                             ______________________________________                                    

The ingredients are blended, hammer-milled until all the solids areessentially under 50 microns, reblended, and packaged.

EXAMPLE 9

Wettable Powder

    ______________________________________                                        N--[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]-3,4-                                                       50%                                              dihydro-2H--1-benzothiopyran-8-sulfonamide, 1,1-                              dioxide                                                                       sodium alkylnaphthalenesulfonate                                                                           2%                                               low viscosity methyl cellulose                                                                             2%                                               diatomaceous earth           46%                                              ______________________________________                                    

The ingredients are blended, coarsely hammer-milled and then air-milledto produce particles essentially all below 10 microns in diameter. Theproduct is reblended before packaging.

EXAMPLE 10

Granule

    ______________________________________                                        Wettable Powder of Example 9                                                                            5%                                                  attapulgite granules      95%                                                 (U.S..S. 20-40 mesh; 0.84-0.42 mm)                                            ______________________________________                                    

A slurry of wettable powder containing ≈25% solids is sprayed on thesurface of attapulgite granules in a double-cone blender. The granulesare dried and packaged.

EXAMPLE 11

Extruded Pellet

    ______________________________________                                        N--[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)aminocar-                                                        25%                                             bonyl]-3,4-dihydro-2H--1-benzothiopyran-8-sulfon-                             amide, 1,1-dioxide                                                            anhydrous sodium sulfate      10%                                             crude calcium ligninsulfonate 5%                                              sodium alkylnaphthalenesulfonate                                                                            1%                                              calcium/magnesium bentonite   59%                                             ______________________________________                                    

The ingredients are blended, hammer-milled and then moistened with about12% water. The mixture is extruded as cylinders about 3 mm diameterwhich are cut to produce pellets about 3 mm long. These may be useddirectly after drying, or the dried pellets may be crushed to pass aU.S.S. No. 20 sieve (0.84 mm openings). The granules held on a U.S.S.No. 40 sieve (0.42 mm openings) may be packaged for use and the finesrecycled.

EXAMPLE 12

Oil Suspension

    ______________________________________                                        N--[(4-methoxy-6-methylpyrimidin-2-yl)aminocarbonyl]-                                                       25%                                             3,4-dihydro-2H--1-benzothiopyran-8-sulfonamide, 1,1-                          dioxide                                                                       polyoxyethylene sorbitol hexaoleate                                                                         5%                                              highly aliphatic hydrocarbon oil                                                                            70%                                             ______________________________________                                    

The ingredients are ground together in a sand mill until the solidparticles have been reduced to under about 5 microns. The resultingthick suspension may be applied directly, but preferably after beingextended with oils or emulsified in water.

EXAMPLE 13

Wettable Powder

    ______________________________________                                        N--[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]-3,4-                                                       20%                                              dihydro-2H--1-benzothiopyran-8-sulfonamide, 1,1-                              dioxide                                                                       sodium alkylnaphthalenesulfonate                                                                           4%                                               sodium ligninsulfonate       4%                                               low viscosity methyl cellulose                                                                             3%                                               attapulgite                  69%                                              ______________________________________                                    

The ingredients are thoroughly blended. After grinding in a hammer-millto produce particles essentially all below 100 microns, the material isreblended and sifted through a U.S.S. No. 50 sieve (0.3 mm opening) andpackaged.

EXAMPLE 14

Low Strength Granule

    ______________________________________                                        N--[(4-methoxy-6-methylpyrimidin-2-yl)aminocarbonyl]-                                                       1%                                              3,4-dihydro-2H--1-benzothiopyran-8-sulfonamide, 1,1-                          dioxide                                                                       N,N--dimethylformamide        9%                                              attapulgite granules          90%                                             (U.S.S. 20-40 sieve)                                                          ______________________________________                                    

The active ingredient is dissolved in the solvent and the solution issprayed upon dedusted granules in a double cone blender. After sprayingof the solution has been completed, the blender is allowed to run for ashort period and then the granules are packaged.

EXAMPLE 15

Aqueous Suspension

    ______________________________________                                        N--[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)aminocar-                                                      40%                                               bonyl]-3,4-dihydro-2H--1-benzothiopyran-8-sulfon-                             amide, 1,1-dioxide                                                            polyacrylic acid thickener  0.3%                                              dodecylphenol polyethylene glycol ether                                                                   0.5%                                              disodium phosphate          1%                                                monosodium phosphate        0.5%                                              polyvinyl alcohol           1.0%                                              water                       56.7%                                             ______________________________________                                    

The ingredients are blended and ground together in a sand mill toproduce particles essentially all under 5 microns in size.

EXAMPLE 16

Solution

    ______________________________________                                        N--[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]-3,4-                                                       5%                                               dihydro-2H--1-benzothiopyran-8-sulfonamide, 1,1-                              dioxide, sodium salt                                                          water                        95%                                              ______________________________________                                    

The salt is added directly to the water with stirring to produce thesolution, which may then be packaged for use.

EXAMPLE 17

Low Strength Granule

    ______________________________________                                        N--[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)aminocar-                                                      0.1%                                              bonyl]-3,4-dihydro-2H--1-benzothiopyran-8-sulfon-                             amide, 1,1-dioxide                                                            attapulgite granules        99.9%                                             (U.S.S. 20-40 mesh)                                                           ______________________________________                                    

The active ingredient is dissolved in a solvent and the solution issprayed upon dedusted granules in a double-cone blender. After sprayingof the solution has been completed, the material is warmed to evaporatethe solvent. The material is allowed to cool and then packaged.

EXAMPLE 18

Granule

    ______________________________________                                        N--[(4-methoxy-6-methy1-1,3,5-triazin-2-yl)aminocar-                                                        80%                                             bonyl]-3,4-dihydro-2H--1-benzothiopyran-8-sulfon-                             amide, 1,1-dioxide                                                            wetting agent                 1%                                              crude ligninsulfonate salt (containing                                                                      10%                                             5-20% of the natural sugars)                                                  attapulgite clay              9%                                              ______________________________________                                    

The ingredients are blended and milled to pass through a 100 meshscreen. This material is then added to a fluid bed granulator, the airflow is adjusted to gently fluidize the material, and a fine spray ofwater is sprayed onto the fluidized material. The fluidization andspraying are continued until granules of the desired size range aremade. The spraying is stopped, but fluidization is continued, optionallywith heat, until the water content is reduced to the desired level,generally less than 1%. The material is then discharged, screened to thedesired size range, generally 14-100 mesh (1410-149 microns), andpackaged for use.

EXAMPLE 19

High Strength Concentrate

    ______________________________________                                        N--[(4-methoxy-6-methylpyrimidin-2-yl)aminocarbonyl]-                                                       99%                                             3,4-dihydro-2H--1-benzothiopyran-8-sulfonamide, 1,1-                          dioxide                                                                       silica aerogel                0.5%                                            synthetic amorphous silica    0.5%                                            ______________________________________                                    

The ingredients are blended and ground in a hammer-mill to produce amaterial essentially all passing a U.S.S. No. 50 screen (0.3 mmopening). The concentrate may be formulated further if necessary.

EXAMPLE 20

Wettable Powder

    ______________________________________                                        N--[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl] -3,4-                                                      90%                                              dihydro-2H--1-benzothiopyran-8-sulfonamide, 1,1-                              dioxide                                                                       dioctyl sodium sulfosuccinate                                                                              0.1%                                             synthetic fine silica        9.9%                                             ______________________________________                                    

The ingredients are blended and ground in a hammer-mill to produceparticles essentially all below 100 microns. The material is siftedthrough a U.S.S. No. 50 screen and then packaged.

EXAMPLE 21

Wettable Powder

    ______________________________________                                        N--[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)aminocar-                                                        40%                                             bonyl]-3,4-dihydro-2H--1-benzothiopyran-8-sulfon-                             amide, 1,1-dioxide                                                            sodium ligninsulfonate        20%                                             montmorillonite clay          40%                                             ______________________________________                                    

The ingredients are thoroughly blended, coarsely hammer-milled and thenair-milled to produce particles essentially all below 10 microns insize. The material is reblended and then packaged.

EXAMPLE 22

Oil Suspension

    ______________________________________                                        N--[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]-3,4-                                                       35%                                              dihydro-2H--1-benzothiopyran-8-sulfonamide, 1,1-                              dioxide                                                                       blend of polyalcohol carboxylic                                                                            6%                                               esters and oil soluble petroleum                                              sulfonates                                                                    xylene                       59%                                              ______________________________________                                    

The ingredients are combined and ground together in a sand mill toproduce particles essentially all below 5 microns. The product can beused directly, extended with oils, or emulsified in water.

EXAMPLE 23

Dust

    ______________________________________                                        N--[(4-methoxy-6-methylpyrimidin-2-yl)aminocarbonyl]-                                                       10%                                             3,4-dihydro-2H--1-benzothiopyran-8-sulfonamide, 1,1-                          dioxide                                                                       attapulgite                   10%                                             Pyrophyllite                  80%                                             ______________________________________                                    

The active ingredient is blended with attapulgite and then passedthrough a hammer-mill to produce particles substantially all below 200microns. The ground concentrate is then blended with powderedpyrophyllite until homogeneous.

Utility

The compounds of the present invention are active herbicides. They haveutility for broadspectrum pre- and/or post-emergence weed control inareas where complete control of all vegetation is desired, such asaround fuel storage tanks, ammunition depots, industrial storage areas,parking lots, drivein theaters, around billboards, highway and railroadstructures. Alternatively, the compounds may be used to modify plantgrowth.

The rates of application for the compounds of the invention aredetermined by a number of factors, including their use as growthmodifiers, the crop species involved, the types of weeds to becontrolled, weather and climate, formulations selected, mode ofapplication, amount of foliage present, etc. In general terms, thesubject compounds should be applied at levels of around 0.125 to 10kg/ha, the lower rates being suggested for use on lighter soils and/orthose having a low organic matter content, for growth modification orfor situations where only short-term persistence is required.

The compounds of the invention may be used in combination with any othercommercial herbicide examples of which are those of the triazine,triazole, uracil, urea, amide, diphenylether, carbamate and bipyridyliumtypes.

The herbicidal properties of the subject compounds were discovered in anumber of greenhouse tests. The test procedures and results follow.

Test A

Seeds of crabgrass (Digitaria sp.), barnyardgrass (Echinochloacrusgalli), wild oats (Avena fatua), sicklepod (Cassia obtusifolia),morningglory (Ipomoea sp.), cocklebur (Xanthium sp.), sorghum, corn,soybean, sugar beet, rice, wheat and nutsedge tubers (Cyperus rotundus)were planted in a growth medium and treated pre-emergence with thechemicals dissolved in a non-phytotoxic solvent. At the same time, thesecrop and weed species, along with cotton and bush bean, were treatedwith a soil/foliage application. At the time of treatment, the plantsranged in height from 2 to 18 cm. Treated plants and controls weremaintained in a greenhouse for sixteen days, after which all specieswere compared to controls and visually rated for response to treatment.The ratings, summarized in Table A, are based on a numerical scaleextending from 0=no injury, to 10=complete kill. The accompanyingdescriptive symbols have the following meanings:

C=chlorosis/necrosis;

E=emergence inhibition;

G=growth retardation;

H=formative effects;

U=unusual pigmentation;

X=axillary stimulation; and

6Y=abscised buds or flowers. ##STR47##

                                      TABLE A                                     __________________________________________________________________________            Cmpd. 1                                                                             Cmpd. 2                                                                             Cmpd. 3                                                                             Cmpd. 4                                                                             Cmpd. 4                                                                             Cmpd. 5                                 Rate, kg/ha                                                                           0.05  0.05  0.05  0.05  0.4   0.05                                    __________________________________________________________________________    POST-EMERGENCE                                                                Bush bean                                                                             3C,6Y 5C,9G,6Y                                                                            5C,9G,6Y                                                                            5C,8G,6Y                                                                            4C,8G,6Y                                                                            0                                       Cotton  1C    2C,5G 2C,4G 2C,6G 4C,8G 0                                       Morningglory                                                                          2C    5C,9G 5C,9G 2C,5G 4C,5H 0                                       Cocklebur                                                                             1C    5C,9G 5C,9G 1H    4C,8H 0                                       Sicklepod                                                                             1C    4C,8G 5C,9G 0     1C    0                                       Nutsedge                                                                              0     1C    1C,5G 0     0     0                                       Crabgrass                                                                             0     4C,6G 5C,9H 2G    3C,8G 0                                       Barnyardgrass                                                                         1C,3H 5C,9H 5C,9H 8H    5C,8H 0                                       Wild Oats                                                                             0     5C,9G 5C,9G 2C,8G 4C,8G 0                                       Wheat   1C    2C,9G 4C,9G 2C,8G 4U,9G 0                                       Corn    0     3C,9G 4C,9G 3C,9G 3U,9G 0                                       Soybean 1C    4C,9G,5X                                                                            3C,8G 2C,3H 2C,7G 0                                       Rice    2G    5C,9G 6C,9G 5C,9G 5C,9G 0                                       Sorghum 1C,4G 4C,9G 1C,9G 3C,9G 2C,9G 0                                       Sugar beet                                                                            2C,4G 4C,8G 9C    2C,3H 3C,3H 0                                       PRE-EMERGENCE                                                                 Morningglory                                                                          0     4C,6H 9G    2C    4C,6H 0                                       Cocklebur                                                                             0     9H    9H    --    9H    0                                       Sicklepod                                                                             0     3C    2C,8G 0     3C,6H 0                                       Nutsedge                                                                              0     1C    2C,3G 0     0     0                                       Crabgrass                                                                             0     2C,4G 2C,5G 0     1C,5G 0                                       Barnyardgrass                                                                         0     2C,5G 3C,9H 1C    2C,8H 0                                       Wild Oats                                                                             0     4C,6G 5C,9G 1C,4G 4C,9G 0                                       Wheat   0     3C,9G 2C,9H 1C,5G 3C,9G 0                                       Corn    0     4C,8G 3C,9G 2C,4G 2C,9G 0                                       Soybean 0     3C,2H 3C,3H 2G    2C,3H 0                                       Rice    0     2C,3G 10E   2C,4G 10E   0                                       Sorghum 0     5C,9H 5C,9G 2C,8G 9H    0                                       Sugar beet                                                                            0     2C,4G 10E   3C,8G 7G    0                                       __________________________________________________________________________            Cmpd. 5                                                                            Cmpd. 6                                                                            Cmpd. 6                                                                            Cmpd. 7                                                                            Cmpd. 7                                                                            Cmpd. 8                                                                            Cmpd. 8                                 Rate, kg/ha                                                                           2    0.05 2    0.05 2    0.05 2                                       __________________________________________________________________________    POST-EMERGENCE                                                                Bush bean                                                                             1C   0    0    0    1C   0    0                                       Cotton  2C   0    1C   0    4C,4H                                                                              0    1C                                      Morningglory                                                                          3C   0    1C   0    2C,2H                                                                              0    0                                       Cocklebur                                                                             2C   0    1C   0    1C,5G                                                                              0    2G                                      Sicklepod                                                                             0    0    0    0    1C   0    0                                       Nutsedge                                                                              0    0    0    0    0    0    0                                       Crabgrass                                                                             2C,3G                                                                              0    2C,4G                                                                              0    3C,6G                                                                              0    0                                       Barnyardgrass                                                                         2C   0    1C   0    3C,9H                                                                              0    0                                       Wild Oats                                                                             0    0    0    0    2C,8G                                                                              0    0                                       Wheat   0    0    0    0    2C,7G                                                                              0    0                                       Corn    3C,4G                                                                              0    0    0    2C,8H                                                                              0    2G                                      Soybean 2C   0    1C   0    0    0    0                                       Rice    3C   0    2C,5G                                                                              0    2C,8G                                                                              0    0                                       Sorghum 3C,5G                                                                              0    2C,5H                                                                              0    2C,9G                                                                              0    1C                                      Sugar beet                                                                            3C   0    1C   0    1C   0    0                                       PRE-EMERGENCE                                                                 Morningglory                                                                          2C,7H                                                                              0    8G   0    8H   0    2C,7H                                   Cocklebur                                                                             8H   0    8H   0    9H   0    9H                                      Sicklepod                                                                             3C   0    2C,6G                                                                              0    0    0    1C                                      Nutsedge                                                                              2C,7G                                                                              0    8G   0    3G   0    10E                                     Crabgrass                                                                             2C,4G                                                                              0    2G   0    0    0    1C                                      Barnyardgrass                                                                         3C,8H                                                                              0    2C,8H                                                                              0    3C,9H                                                                              0    2C,3H                                   Wild Oats                                                                             4C,8G                                                                              0    2C,9G                                                                              0    2C,5G                                                                              0    0                                       Wheat   2C,8G                                                                              0    2C,9G                                                                              0    2C,9G                                                                              0    3G                                      Corn    3C,9H                                                                              0    2C,8G                                                                              0    2C,8G                                                                              0    3C,6H                                   Soybean 2C,2H                                                                              0    2C,2H                                                                              0    1C   0    0                                       Rice    4C,9H                                                                              0    5C,9H                                                                              0    9H   0    8H                                      Sorghum 4C,9G                                                                              0    2C,9G                                                                              0    3C,9G                                                                              0    2C,9G                                   Sugar beet                                                                            5C,9G                                                                              0    4C,8G                                                                              0    5G   0    4G                                      __________________________________________________________________________     Test B

Two plastic bulb pans were filled with fertilized and limed Woodstownsandy loam. One pan was planted with corn, sorghum, Kentucky bluegrassand several grass weeds. The other pan was planted with cotton,soybeans, purple nutsedge (Cyperus rotundus), and several broadleafweeds. The following grassy and broadleaf weeds were planted: crabgrass(Digitaria sanguinalis), barnyardgrass (Echinochloa crusgalli), wildoats (Avena fatua), johnsongrass (Sorghum halepense), dallisgrass(Paspalum dilatatum), giant foxtail (Setaria faberii), cheatgrass(Bromus secalinus), mustard (Brassica arvensis), cocklebur (Xanthiumpensylvanicum), morningglory (Ipomoea hederacea), sicklepod (Cassiaobtusifolia), teaweed (Sida spinosa), velvetleaf (Abutilon theophrasti),and jimsonweed (Datura stramonium). A 12.5 cm diameter plastic pot wasalso filled with prepared soil and planted with rice and wheat. Another12.5 cm pot was planted with sugar beets. The above four containers weretreated pre-emergence with several test compounds within the scope ofthe invention.

Twenty-eight days after treatment, the plants were evaluated andvisually rated for response to the chemical treatments utilizing therating system described previously for Test A. The data are summarizedin Table B.

                  TABLE B                                                         ______________________________________                                        PRE-EMERGENCE ON                                                              WOODSTOWN SANDY LOAM                                                                     Compound 2 Compound 3  Compound 4                                  Rate, kg/ha                                                                              0.03   0.12    0.03  0.12  0.06 0.25                               ______________________________________                                        Crabgrass  0      2G      0     3G    0    0                                  Barnyardgrass                                                                            0      2G      2G    3G    2G   2G                                 Sorghum    0      8G      6G    9G    8G   9G                                 Wild Oats  0      4G      2G    8G    5G   8G                                 Johnsongrass                                                                             0      4G      7G    9G    4G   8G                                 Dallisgrass                                                                              0      2G      0     9G    0    5G                                 Giant foxtail                                                                            0      5G      0     8G    4G   6G                                 Ky. bluegrass                                                                            0      8G      7G    9G    5G   9G                                 Cheatgrass 0      7G      6G    9G    4G   8G                                 Sugar beets                                                                              0      5G      2G    7G    3G   5G                                 Corn       0      2G      2G    7G    2G   8G                                 Mustard    0      7G      3G    9G    8G   9G                                 Cocklebur  0      2G      0     2G    0    3G                                 Pigweed    --     --      --    --    --   --                                 Nutsedge   0      0       0     2G    4G   6G                                 Cotton     0      0       0     2G    0    0                                  Morningglory                                                                             0      0       0     6G    0    0                                  Sicklepod  0      0       0     5G    0    0                                  Teaweed    0      0       0     2G    0    0                                  Velvetleaf 0      0       0     6G    0    0                                  Jimsonweed 0      0       0     5G    0    0                                  Soybean    0      0       0     0     0    0                                  Rice       2G     9G      8G    10C   9G   9G                                 Wheat      2G     5G      5G    7G    0    0                                  ______________________________________                                    

What is claimed is:
 1. A compound selected from ##STR48## wherein J is##STR49## Q is O, S or SO₂ ; R is H or CH₃ ;R₁ is H, CH₃, OCH₃, Cl, Br,CO₂ R₅, SO₂ R₆, OSO₂ R₇ or SO₂ NR₈ R₉ ; R₄ is H or CH₃ ; R₂ and R₃ areindependently H or C₁ -C₃ alkyl; R₅ is C₁ -C₃ alkyl, CH₂ CH═CH₂, CH₂ CH₂OCH₃ or CH₂ CH₂ Cl; R₆ is C₁ -C₃ alkyl; R₇ is C₁ -C₃ alkyl or CF₃ ; R₈and R₉ are independently C₁ -C₂ alkyl; A is ##STR50## X is CH₃ or OCH₃ ;Y is CH₃, OCH₃, OC₂ H₅, CH₂ OCH₃, NH₂, NHCH₃ or N(CH₃)₂ ; Z is N;andtheir agriculturally suitable salts provided that (1) the totalnumber of carbon atoms in R₂ and R₃ are less than or equal to 3; (2) inFormula J₂, when R₂ and R₃ is other than H, then R₄ is H; (3) in FormulaJ₃ when R₂ is other than H, then R₄ is H; (4) when Q is S, then R₁ isnot SO₂ NR₈ R₉ ; (5) in Formula J₃ and J₆, Q may not be O; and (6) inFormula J₇, R₁ is not CH₃.
 2. Compounds of claim 1 wherein J is J₁. 3.Compounds of claim 2 where R is H.
 4. Compounds of claim 3 where R₁ isH.
 5. Compounds of claim 4 where Y is CH₃ or OCH₃.
 6. Compounds of claim1 where J is J₂.
 7. Compounds of claim 6 where R is H.
 8. Compounds ofclaim 7 where R₁ is H.
 9. Compounds of claim 8 where Y is OCH₃ or CH₃.10. Compounds of claim 1 where J is J₃.
 11. Compounds of claim 10 whereR is H.
 12. Compounds of claim 11 where R₁ is H.
 13. Compounds of claim12 where Y is OCH₃ or CH₃.
 14. Compounds of claim 1 where J is J₄. 15.Compounds of claim 14 where R is H.
 16. Compounds of claim 15 where R₁is H.
 17. Compounds of claim 16 where Y is OCH₃ or CH₃.
 18. Compounds ofclaim 1 where J is J₅.
 19. Compounds of claim 18 where R is H. 20.Compounds of claim 19 where R₁ is H.
 21. Compounds of claim 20 where Yis OCH₃ or CH₃.
 22. Compounds of claim 1 where J is J₆.
 23. Compounds ofclaim 22 where R is H.
 24. Compounds of claim 23 where R₁ is H. 25.Compounds of claim 24 where Y is OCH₃ or CH₃.
 26. Compounds of claim 1where J is J₇.
 27. Compounds of claim 26 where R is H.
 28. Compounds ofclaim 27 where R₁ is H.
 29. Compounds of claim 28 where Y is OCH₃ orCH₃.
 30. The compound of claim 1 which isN-[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)aminocarbonyl]-3,4-dihydro-2H-1-benzothiopyran-8-sulfonamide,1,1-dioxide.
 31. A composition suitable for controlling the growth ofundesired vegetation which comprises an effective amount of a compoundof claim 1 and at least one of the following: surfactant, solid orliquid diluent.
 32. A composition suitable for controlling the growth ofundesired vegetation which comprises an effective amount of a compoundof claim 2 and at least one of the following: surfactant, solid orliquid diluent.
 33. A composition suitable for controlling the growth ofundesired vegetation which comprises an effective amount of a compoundof claim 3 and at least one of the following: surfactant, solid orliquid diluent.
 34. A composition suitable for controlling the growth ofundesired vegetation which comprises an effective amount of a compoundof claim 4 and at least one of the following: surfactant, solid orliquid diluent.
 35. A composition suitable for controlling the growth ofundesired vegetation which comprises an effective amount of a compoundof claim 5 and at least one of the following: surfactant, solid orliquid diluent.
 36. A method for controlling the growth of undesiredvegetation which comprises applying to the locus to be protected aneffective amount of a compound of claim
 1. 37. A method for controllingthe growth of undesired vegetation which comprises applying to the locusto be protected an effective amount of a compound of claim
 2. 38. Amethod of controlling the growth of undesired vegetation which comprisesapplying to the locus to be protected an effective amount of a compoundof claim
 3. 39. A method for controlling the growth of undesiredvegetation which comprises applying to the locus to be protected aneffective amount of a compound of claim
 4. 40. A method for controllingthe growth of undesired vegetation which comprises applying to the locusto be protected an effective amount of a compound of claim 5.